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# Contents

## 1 Introduction

It is by now well established that gauge theories can be described by strings, representing their flux lines. These strings, however, are unusual. In the case of the pure glue gauge theory they propagate in a five dimensional warped space  and, if some other fields are present, even in higher dimensions. The string Lagrangian is that of the non-linear sigma model with the target space coinciding with the one described above. The simplest and best explored case of this gauge/string duality is presented by the Yang-Mills theory with $`𝒩=4`$ supersymmetry. Conformal invariance and other symmetries of this theory unambiguously determine the geometry of the warped target space. It was found in , developing some earlier findings of , that the desired string theory in this case lives in the space $`AdS_5\times S^5`$ and that there is a unique prescription relating physical quantities in the string and gauge pictures. Many more complicated examples have been analyzed since then, confirming the existence of a dual string picture for various gauge theories.

However, until very recently, it is mostly the supergravity limit (corresponding to the one-loop approximation of the sigma model) that has been tested, basically because of the challenges inherent in formulating the appropriate sigma models111See  and references therein for the most highly developed approach to this problem. and of solving them once they are formulated. It has been recently pointed out in  that for gauge theory operators with very high bare dimension, such as operators with high spin, R-charge, etc., the supergravity approximation is inadequate even at small curvatures of the AdS (corresponding to large ’t Hooft coupling $`\lambda =g_{\mathrm{YM}}^2N`$). It is expected that for for certain classes of such operators the dimensions asymptotically become integer spaced, even when $`\lambda 1`$.

These expectations were confirmed and considerably strengthened in  for a special class of operators with high R-charge. It turned out to be possible in this case to approximate the AdS space by the much simpler and exactly solvable pp-wave  by taking the Penrose limit . What remained unclear was whether this success is a manifestation of a general mechanism.

In this paper we will argue that the gauge theory states with large quantum numbers are described by certain solitons of the nonlinear sigma model. The reason for this is easy to explain. The world sheet dimensions of the 2d conformal field theories are expressed in the radial quantization scheme as eigenvalues of the hamiltonian $`H=L_0+\overline{L_0}.`$ For the small sigma model coupling, the spectrum of such a hamiltonian contains the usual perturbative oscillations which are effectively described in the target space by the supergravity approximation.

However in some cases (which we discuss below) there are also soliton states with world sheet dimensions $`\frac{1}{\alpha }`$ where $`\alpha =1/\sqrt{\lambda }`$ is the sigma model coupling. Discussion of these “conformal solitons” and their gauge counterparts is the main content of the present paper. There is already a well known application of classical solutions: the calculation of the Wilson loop . For closed loops, the relevant solutions (minimal surfaces in $`AdS_5`$) are instanton-like, having a finite action once a divergence associated to point-like charges is regulated. Our solutions, by contrast, are solitons, and they have different physical meaning. They describe operators with high bare dimensions (very long “words” in the terminology of ). Similar operators describe asymptotic behavior of the deep inelastic scattering.

An important result, which is responsible for some of the phenomenological successes of perturbative QCD in deep inelastic scattering, is the logarithmic dependence of anomalous dimension on spin for high-spin gauge theory operators . With the (relatively) new techniques of AdS/CFT correspondence in hand  (for a review see ), we might ask how (and whether) logarithmic scaling violations might arise in a regime where stringy techniques in anti-de Sitter space are well-controlled. On the field theory side, such effects need not be tied to a non-zero beta-function: anomalous dimensions of non-chiral operators can arise even in a superconformal theory like $`𝒩=4`$ super-Yang-Mills. On the string theory side, it might seem difficult to make progress, because gauge theory operators which are neither chiral nor descendants of chiral operators are thought to correspond to excited string states rather than supergravity modes. Such states have masses at least of order $`1/\sqrt{\alpha ^{}}`$, so their dimensions typically grow as $`\lambda ^{1/4}`$ . Full control of the string spectrum in $`AdS_5\times S^5`$ and the operator-state map seems to be beyond our grasp at present. However, we will argue that certain features of the string spectrum can be well-understood from a non-linear sigma-model perspective, which bypasses (or at least postpones) the usual difficulty with Ramond-Ramond backgrounds.

We will consider a class of gauge invariant operators with high Lorentz spin $`S`$. These operators are quite different from those with large R-charge: their presence does not rely on the supersymmetry of the gauge theory. In fact, they are well-known to be present in QCD where they were studied early on in the context of deep inelastic scattering . Analogous operators are present in the $`𝒩=4`$ supersymmetric $`SU(N)`$ gauge theory, for example,

$`trX^I_{(\mu _1}\mathrm{}_{\mu _s)}X^I.`$   (1)
In free field theory, such an operator would have “twist two:” that is, its dimension is $`S+2`$, while its space-time spin is $`S`$. Similar operators play an important role in deep inelastic scattering, where leading weak coupling corrections of the form $`\mathrm{\Delta }=(S+2)+c_1g_{YM}^2N\mathrm{ln}S`$ can be probed experimentally. Unlike the operators with large R-charge, such high-spin operators cannot be chiral or ‘nearly chiral,’ hence their anomalous dimensions would seem to be difficult to control at strong coupling. Nevertheless, for sufficiently large $`S`$, we present a simple semi-classical method for calculating them. Our approach involves finding a soliton solution of the $`\sigma `$-model describing type IIB strings on $`AdS_5\times S^5`$. Although a solution of such a RR $`\sigma `$-model is lacking, finding the solitons describing the high-spin closed strings is a much easier problem.

Consider, for example, closed strings on the leading Regge trajectory, i.e. those with the smallest mass for a given spin $`S`$. It is well known that an approximate description of such states in flat space is a folded closed string which spins as a rigid rod around its center. To study the gauge theory we simply replace the flat space by the global $`AdS_5`$ metric,

$$ds^2=R^2\left(dt^2\mathrm{cosh}^2\rho +d\rho ^2+\mathrm{sinh}^2\rho d\mathrm{\Omega }_3^2\right),$$
(2)
and consider a spinning folded closed string whose center lies at rest at $`\rho =0`$.222We are grateful to Juan Maldacena for suggesting this to us. In the AdS4 case such a solution was constructed and studied in . We take the usual large $`N`$ ‘t Hooft limit keeping $`\lambda =g_{\mathrm{YM}}^2N`$ fixed, and make $`\lambda `$ very large so that the curvature of the metric is small. For spin $`S\sqrt{\lambda }`$ we show that the standard AdS/CFT analysis of operator dimensions  applies. For $`S\sqrt{\lambda }`$, however, this analysis becomes inadequate because the string gets appreciably stretched across AdS5. Identifying the energy in the global coordinates with the conformal dimension in the dual gauge theory, we find for $`S\sqrt{\lambda }`$,

$`\mathrm{\Delta }S={\displaystyle \frac{\sqrt{\lambda }}{\pi }}\mathrm{ln}(S/\sqrt{\lambda })+O(S^0).`$   (3)
The result (3) is interesting because these anomalous dimensions grow logarithmically with spin only in gauge theories . Details of the calculation leading to (3) will be provided in section 3 (the logarithmic growth of $`\mathrm{\Delta }S`$ on the AdS side is closely related to the $`\mathrm{ln}S`$ scaling of the proper length of the string for large $`S`$). The result (3) shows that for these states the anomalous dimension is small compared to the bare one:

$`{\displaystyle \frac{\mathrm{\Delta }S}{S}}{\displaystyle \frac{\mathrm{ln}(S/\sqrt{\lambda })}{S/\sqrt{\lambda }}}1.`$   (4)
Comparison with the perturbative results motivates the following formula for the leading term in the dimension of a high-spin operator on the leading Regge trajectory:

$$\mathrm{\Delta }S=f(\lambda )\mathrm{ln}S,$$
(5)
where $`f(\lambda )=a_1\lambda +a_2\lambda ^2+\mathrm{}`$ is a certain function of the ’t Hooft coupling. Indeed, in many gauge theories (including non-supersymmetric ones!) it has been argued that the leading term in the anomalous dimensions grows as $`\mathrm{ln}S`$ to all orders in perturbation theory, and probably also non-perturbatively .333 We are grateful to G. Korchemsky for bringing these papers to our attention, and for helpful comments after the original version of this paper appeared. The analysis of  is based on studying Wilson loops with cusps, and the function $`f(\lambda )`$ appears in this approach as the “cusp anomalous dimension.” Therefore, the formula (5) may be a new point of contact between gauge theory and string theory.

Although we discuss operators with high Lorentz spin in the most detail, we believe that our approach of identifying highly excited gauge theory operators with $`\sigma `$-model solitons is quite general and can be applied to other kinds of operators. Our techniques may also be generalized to backgrounds describing non-conformal gauge theories.

The organization of the paper is as follows. In section 2, we re-examine the case of large R-charge, obtaining the results of  from a different perspective, developing ideas in . In section 3, we use similar methods to treat spinning strings in $`AdS_5`$. In section 4 we study some other examples of highly excited strings. And in section 5 we review the appearance of logarithmic scaling violations in perturbative gauge theory and discuss the relation with the results of section 3.

## 2 Large R-charge revisited

Our work is largely inspired by the recent important observation that, if the bare dimension of an operator becomes large simultaneously with $`\lambda `$, then the standard rule that the anomalous dimension blows up as $`\lambda ^{1/4}`$ may be violated . A simple example of such a modification is provided by certain operators whose R-charge $`J`$ is of order $`\sqrt{\lambda }`$. In  it was shown that such operators are in one-to-one correspondence with all type IIB string states in a RR-charged pp wave background which is a Penrose limit of $`AdS_5\times S^5`$ . Exact solvability of string theory in this pp wave background , together with the AdS/CFT correspondence, predict that the dimensions of these operators are given by

$$\mathrm{\Delta }=J+\underset{n=\mathrm{}}{\overset{\mathrm{}}{}}N_n\sqrt{1+\frac{\lambda n^2}{J^2}},$$
(6)
where $`N_n`$ is the excitation number of the $`n`$-th string mode. The operators with $`N_n=0`$ for all $`n0`$ are chiral while all the rest are non-chiral. Nevertheless, in the limit $`\lambda \mathrm{}`$, where $`J^2/\lambda `$ is held fixed, it is found that the anomalous dimension becomes negligible compared to the bare dimension, $`(\mathrm{\Delta }J)/J0`$.

In this section we will reconsider the case of the large R charge. We will treat it differently (but with the same results) in order to set the stage for the more complicated cases. The bosonic part of the action describing the AdS$`{}_{5}{}^{}\times S_5`$ sigma model is given by

$$S=\frac{1}{2\alpha }d^2\sigma \sqrt{g}((_\alpha n)^2+(_\alpha N)^2)+\mathrm{}$$
(7)
where $`n`$ is a unit vector describing $`S^5`$ and $`N`$ is a hyperbolic unit vector describing $`AdS_5`$. The dots stand for the fermionic and RR terms. The sigma model coupling $`\alpha `$ is related to $`\lambda `$ as $`\alpha =\frac{1}{\sqrt{\lambda }}.`$ Let us consider the S5 part first. The R charge $`J`$ is the angular momentum on $`S^5`$. The standard perturbative formula for the world sheet dimension $`\delta `$ gives for large $`J`$

$$\delta =\frac{1}{2}\alpha J^2$$
(8)
As was explained in , the AdS part gives the same contribution but with the reversed sign (because of the negative curvature) and thus

$$\delta =\frac{1}{2}\alpha (J^2\mathrm{\Delta }^2)$$
(9)
where $`\mathrm{\Delta }`$ is the space-time dimension. The mass shell condition is given by $`\delta =l+1,`$ where $`l`$ is the “level,” that is the number of the world sheet derivatives in the corresponding operator. From this we see that there should exist gauge theory operators with $`\mathrm{\Delta }`$ and $`J`$ of order $`1/\alpha `$ but with $`\mathrm{\Delta }J`$ of order $`1`$. However, we have to correct the above formula by accounting for the terms in the world-sheet dimension containing the powers of $`\alpha J1,`$ while neglecting the powers of $`\alpha .`$ In order to fix the angular momentum we will consider the hamiltonian in the rotating frame $`\stackrel{~}{H}=H\omega `$ $`J`$ and look for the minimal energy. This procedure is equivalent to considering the classical solution for the $`S^5`$ sigma model

$$\theta =0,\psi =\omega \tau ,$$
(10)
where $`\theta `$ and $`\psi `$ are the polar and azimuthal angles on $`S^2`$ (we disregard other angles of $`S^5`$ , which later will give some trivial modification of our formulae); we parametrize the world sheet by the variables $`\tau `$ and $`\sigma `$. Geometrically this solution represents a closed string collapsed to a point which rotates around the equator. The world sheet energy of the above solution is given by $`\frac{1}{2\alpha }\omega ^2`$ which gives the formula (8) after using the relation $`J=\frac{E}{\omega }`$. To account for the corrections mentioned above, it is sufficient to consider harmonic oscillations near this solution. The Lagrangian for the $`\theta `$ oscillations, as seen from (7), has the form

$$\alpha L=\frac{1}{2}\left[(\theta )^2+\omega ^2\mathrm{cos}^2\theta \right]\frac{1}{2}\left[\left(\theta \right)^2\omega ^2\theta ^2+\omega ^2\right].$$
(11)
From here we derive the oscillator spectrum of anomalous dimensions of the spherical sigma model

$$\delta =\frac{\alpha }{2}J^2+\underset{n}{}N_n\sqrt{n^2+\alpha ^2J^2}$$
(12)
where we used the relation $`J=\omega /\alpha `$. The $`N_n`$ here is the excitation number of the n-th oscillator. The formula for AdS part is obtained by the change $`\alpha `$ to $`\alpha `$. The on-shell condition

$$\delta (S^5)+\delta (AdS_5)0$$
(13)
gives the formula (6), which was previously derived in  by the use of the Penrose limit. We see that from the sigma model point of view it corresponds to a harmonic approximation to a relatively trivial classical solution (10). We shall now proceed to the more complicated solutions, describing operators with high spin.

## 3 Leading Regge Trajectory

In this section we consider a spinning closed string in $`AdS_5`$ to understand the relation between dimension and spin for leading Regge trajectory closed strings. To carry out this calculation it is convenient to use the global $`AdS_5`$ metric (2), so that the energy is identified with the conformal dimension in the dual CFT. The string is at the equator of $`S^3`$ and the azimuthal angle depends on time:

$`\varphi =\omega t.`$   (14)
In the Nambu action for the string we pick a gauge where $`\tau =t`$ and $`\rho `$ is a function of $`\sigma `$. The Lagrangian becomes

$$L=4\frac{R^2}{2\pi \alpha ^{}}_0^{\rho _0}𝑑\rho \sqrt{\mathrm{cosh}^2\rho (\dot{\varphi })^2\mathrm{sinh}^2\rho }$$
(15)
The maximum radial coordinate is $`\rho _0`$, and the factor of 4 comes since there are four segments of the string stretching from 0 to $`\rho _0`$, which is determined by

$$\mathrm{coth}^2\rho _0=\omega ^2.$$
(16)
The energy and the spin of the string are

$$E=4\frac{R^2}{2\pi \alpha ^{}}_0^{\rho _0}𝑑\rho \frac{\mathrm{cosh}^2\rho }{\sqrt{\mathrm{cosh}^2\rho \omega ^2\mathrm{sinh}^2\rho }}$$
(17)
$$S=4\frac{R^2}{2\pi \alpha ^{}}_0^{\rho _0}𝑑\rho \frac{\omega \mathrm{sinh}^2\rho }{\sqrt{\mathrm{cosh}^2\rho \omega ^2\mathrm{sinh}^2\rho }}$$
(18)
The same expressions can also be derived in the conformal gauge where the world sheet action is

$$S=\frac{1}{4\pi \alpha ^{}}𝑑\tau 𝑑\sigma G_{ij}_\alpha X^i^\alpha X^j.$$
(19)
Now we need to impose the conditions

$`T_{++}`$ $`=_+X^i_+X^jG_{ij}=0`$  $`T_{}`$ $`=_{}X^i_{}X^jG_{ij}=0.`$   (20)
Inserting $`t=e\tau `$, $`\varphi =e\omega \tau `$, $`\rho =\rho (\sigma )`$ into these equations, we find

$$(\rho ^{})^2=e^2(\mathrm{cosh}^2\rho \omega ^2\mathrm{sinh}^2\rho ).$$
(21)
Thus,

$$d\sigma =\frac{d\rho }{e\sqrt{\mathrm{cosh}^2\rho \omega ^2\mathrm{sinh}^2\rho }}.$$
(22)
We may now adjust $`e`$ so that the period of $`\sigma `$ is $`2\pi `$.

The space-time energy is given by

$`E={\displaystyle \frac{R^2}{2\pi \alpha ^{}}}e{\displaystyle _0^{2\pi }}𝑑\sigma \mathrm{cosh}^2\rho ,`$   (23)
and the spin by

$`S={\displaystyle \frac{R^2}{2\pi \alpha ^{}}}e\omega {\displaystyle _0^{2\pi }}𝑑\sigma \mathrm{sinh}^2\rho .`$   (24)
Changing the integration variable from $`\sigma `$ to $`\rho `$ we find the previously derived expressions.

Since $`R^4=\lambda \alpha ^2`$, where $`\lambda `$ is the ’t Hooft coupling, these expressions specify $`E/\sqrt{\lambda }`$ and $`S/\sqrt{\lambda }`$ as functions of $`\omega `$. Therefore, the dependence of $`E/\sqrt{\lambda }`$ on $`S/\sqrt{\lambda }`$ is known in parametric form. Actually, the integrals in (17) and (18) can be expressed in terms of elliptic or hypergeometric functions, as we shall explain in section 4.3. Here it will suffice to give approximate expressions in the limits where the string is much shorter or much longer than the radius of curvature of $`AdS_5`$.

Short strings. For large $`\omega `$, $`\rho _01/\omega `$. Here the string is not stretched much compared to the radius of curvature of $`AdS_5`$, so we can approximate $`AdS_5`$ by flat metric near the center. The calculation reduces to the standard spinning string in flat space, and we get

$$E=\frac{R^2}{\alpha ^{}\omega },S=\frac{R^2}{2\alpha ^{}\omega ^2},$$
(25)
so that

$$E^2=R^2\frac{2S}{\alpha ^{}}.$$
(26)
Using the AdS/CFT correspondence, we have $`\mathrm{\Delta }=E`$. For large $`\omega `$, $`S\sqrt{\lambda }`$. In this regime we find agreement with the AdS/CFT result

$$\mathrm{\Delta }^2m^2R^2.$$
(27)
Indeed, for the leading closed string Regge trajectory, $`m^2=\frac{2(S2)}{\alpha ^{}}`$, so the precise factor in (26) agrees with the AdS/CFT formula.

Long strings. The situation where $`S\sqrt{\lambda }`$ corresponds to $`\omega `$ approaching 1 from above:

$$\omega =1+2\eta ,$$
(28)
where $`\eta 1`$. Then $`\rho _0`$ becomes very large, so that the string feels the metric near the boundary of AdS:

$$\rho _0\frac{1}{2}\mathrm{ln}(1/\eta ).$$
(29)
Expanding the integrals for $`E`$ and $`S`$, one finds

$$E=\frac{R^2}{2\pi \alpha ^{}}(\frac{1}{\eta }+\mathrm{ln}(1/\eta )+\mathrm{}),$$
(30)
$$S=\frac{R^2}{2\pi \alpha ^{}}(\frac{1}{\eta }\mathrm{ln}(1/\eta )+\mathrm{}).$$
(31)
It follows that $`ES`$ does not approach a constant in the limit $`S\sqrt{\lambda }`$, but instead behaves as follows:

$$ES=\frac{\sqrt{\lambda }}{\pi }\mathrm{ln}(S/\sqrt{\lambda })+\mathrm{}$$
(32)
Thus, the situation is different from the large R-charge limit: the dependence of the dimension on large spin is more complicated than for large R-charge. The logarithmic asymptotics in (32) are qualitatively the same as in perturbative gauge theories, a topic which we will discuss in section 5.

It may be necessary to take the string coupling very small in order to suppress decay of the long spinning strings into a number of shorter strings corresponding to operators which are chiral primaries or descendants of them. In the strict ‘t Hooft limit, $`g_{\mathrm{str}}0`$, hence these states are stable.

Infinite strings: Although energy and angular momentum diverge as $`\omega 1`$ from above, one may nevertheless consider solutions of the form (14) with $`\omega <1`$: such a solution represents two Wilson loops stretching in opposite directions, with the ends rotating on the equator of $`S^3`$ with velocity $`\omega `$. See figure 1.

## 4 Other macroscopic string states

The approach used in section 3 to treat strings spinning in $`AdS_5`$ can also be used to approximately describe other highly excited string states. In sections 4.1 and 4.2, we present two examples. In section 4.3, as a formal exercise, we extend the discussion to states in the sigma model which do not necessarily satisfy the on-shell conditions.

### 4.1 String Spinning on $`S^5`$

A similar calculation may be done for a string whose center of mass is not moving on $`S^5`$, but which spins around that point and is correspondingly stretched. We lose nothing by assuming that this point is the north pole. Let us write the $`S^5`$ metric as

$$ds^2=d\theta ^2+\mathrm{sin}^2\theta d\varphi ^2+\mathrm{cos}^2\theta d\mathrm{\Omega }_3^2,$$
(33)
and adopt the ansatz $`t=e\tau `$, $`\varphi =e\omega \tau `$, $`\theta =\theta (\sigma )`$. Then from $`T_{++}=T_{}=0`$ we get

$`(\theta ^{})^2=e^2(1\omega ^2\mathrm{sin}^2\theta ).`$   (34)
Thus,

$$d\sigma =\frac{d\theta }{e\sqrt{1\omega ^2\mathrm{sin}^2\theta }}.$$
(35)
We may now adjust $`e`$ so that the period of $`\sigma `$ is $`2\pi `$. The folded closed string is stretched along the $`\theta `$ direction up to $`\theta _0`$ given by

$$\mathrm{sin}\theta _0=\frac{1}{\omega }.$$
(36)
The space-time energy is given by

$$E=\frac{R^2}{2\pi \alpha ^{}}e_0^{2\pi }𝑑\sigma =4\frac{R^2}{2\pi \alpha ^{}}_0^{\theta _0}𝑑\theta \left(1\omega ^2\mathrm{sin}^2\theta \right)^{1/2},$$
(37)
and the R-charge by

$$J=\frac{R^2}{2\pi \alpha ^{}}e\omega _0^{2\pi }𝑑\sigma \mathrm{sin}^2\theta =4\frac{R^2}{2\pi \alpha ^{}}\omega _0^{\theta _0}𝑑\theta \left(1\omega ^2\mathrm{sin}^2\theta \right)^{1/2}\mathrm{sin}^2\theta .$$
(38)
These integrals can be expressed in terms of elliptic or hypergeometric functions, but it would add little to the discussion to present the explicit forms. As before, the interesting regime is when $`\omega `$ approaches $`1`$ from above, $`\omega =1+2\eta `$. As $`\eta 0`$, $`\theta _0\pi /2`$. Both $`E`$ and $`J`$ diverge as $`\mathrm{ln}\eta `$ at leading order while their difference stays finite:

$$EJ\frac{2R^2}{\pi \alpha ^{}}=2\frac{\sqrt{\lambda }}{\pi }.$$
(39)
This is to be contrasted with the string spinning in $`AdS_5`$: there, $`ES\sqrt{\lambda }\mathrm{ln}S`$, while here $`EJ\sqrt{\lambda }`$. We believe that the logarithm is due to the many gauge-covariant derivatives that carry the spin $`S`$ in the dual gauge theory.

As for the strings spinning in $`AdS_5`$, it seems likely that the strings spinning in $`S^5`$ can decay into BPS or almost BPS states: physically, this corresponds to the string breaking and descending from the north pole to the equator. Such processes can be suppressed by taking $`g_{\mathrm{str}}1`$. Also in analogy to strings spinning in $`AdS_5`$, we may continue past the limit $`\omega <1`$, but the solutions again change character: instead of a string doubled back on itself, and stretched out because of its angular momentum, we must now consider a string stretched around a great circle of $`S^5`$, and rotating so that its velocity at the equator of $`S^5`$ is $`\omega `$. Such states are unstable toward “slipping off the side” of the $`S^5`$. The relation (34) still holds, and the energy and angular momentum of these great-circle states may be expressed as

$`E`$ $`=4{\displaystyle \frac{R^2}{2\pi \alpha ^{}}}{\displaystyle _0^{2\pi }}𝑑\theta \left(1\omega ^2\mathrm{sin}^2\theta \right)^{1/2},`$  $`J`$ $`=4{\displaystyle \frac{R^2}{2\pi \alpha ^{}}}\omega {\displaystyle _0^{2\pi }}𝑑\theta \left(1\omega ^2\mathrm{sin}^2\theta \right)^{1/2}\mathrm{sin}^2\theta .`$   (40)
As usual, the integrals can be done in terms of elliptic or hypergeometric functions.

### 4.2 Oscillating String

Now let us consider a closed string which oscillates around the center of $`AdS_5`$. It first expands from the center of $`AdS_5`$, reaches a maximum $`\rho `$ and then recontracts back to zero; then this motion repeats. For such a string, $`\varphi =\sigma `$ and $`\rho =\rho (\tau )`$.

The space-time energy is a constant of motion:

$$E=\frac{R^2}{\alpha ^{}}\frac{dt}{d\tau }\mathrm{cosh}^2\rho .$$
(41)
From $`T_{++}=T_{}=0`$ we find

$$(\dot{\rho })^2+\mathrm{sinh}^2\rho e^2\mathrm{cosh}^2\rho =0,$$
(42)
where $`e=E\alpha ^{}/R^2`$.

The maximum radius of the string is found from

$$\mathrm{sinh}^2(2\rho _0)=4e^2.$$
(43)
Presumably these strings correspond to highly excited sigma model operators. It is fairly clear that the excitation level is related to the amplitude $`\rho _0`$. When $`E/\sqrt{\lambda }`$ is small we find harmonic oscillations of amplitude $`\rho _0`$. Then $`\rho _0^2`$ should be proportional to the excitation level of the oscillation:

$$\rho _0^2\frac{n}{\sqrt{\lambda }},$$
(44)
which insures the validity of the usual AdS/CFT relation between $`\mathrm{\Delta }`$ and the level. It is less clear how to extrapolate to large $`E/\sqrt{\lambda }`$ where the oscillations are no longer small, and it is also mysterious to us precisely what gauge theory operators these states correspond to.

### 4.3 Arbitrary conformal dimension

As a formal exercise, we can generalize the results of section 3 to solutions that don’t obey the constraints, but rather have $`T_{++}=T_{}=\delta 1`$ for some arbitrary conformal dimension $`\delta `$. In this way we hope to get an asymptotic formula of the type $`\alpha \delta =f(\alpha \mathrm{\Delta },\alpha S)`$, for the spinning string in $`AdS_5`$. Such a formula is an approximate scaling form, good when $`\alpha 1`$ but $`\alpha \delta `$, $`\alpha \mathrm{\Delta }`$, and $`\alpha S`$ are finite. Equation 32 is recovered by setting $`\delta =1`$.

From $`T_{++}=T_{}=\delta 1`$, we arrive at a slight modification of our previous treatment of the string spinning in $`AdS_5`$: now

$$\left(\frac{d\rho }{d\sigma }\right)^2=\frac{4(\delta 1)}{R^2}+\mathrm{cosh}^2\rho \omega ^2\mathrm{sinh}^2\rho ,$$
(45)
but the expressions (23) and (24) for the energy and spin are unchanged. The integrals can still be done in terms of hypergeometric functions. The result is best expressed be defining

$$s=\frac{2\pi \alpha ^{}}{R^2}Se=\frac{2\pi \alpha ^{}}{R^2}Ea=\sqrt{1+4(\delta 1)/R^2}.$$
(46)
Then we obtain

$`s`$ $`={\displaystyle \frac{\pi \omega }{\sqrt{\omega ^21}}}{\displaystyle \frac{a^2}{\omega ^21}}{}_{2}{}^{}F_{1}^{}({\displaystyle \frac{1}{2}},{\displaystyle \frac{3}{2}};2;{\displaystyle \frac{a^2}{\omega ^21}}){\displaystyle \frac{a}{\eta }}+{\displaystyle \frac{1}{a}}\mathrm{ln}\eta `$  $`e`$ $`={\displaystyle \frac{2\pi }{\sqrt{\omega ^21}}}{}_{2}{}^{}F_{1}^{}({\displaystyle \frac{1}{2}},{\displaystyle \frac{1}{2}};1;{\displaystyle \frac{a^2}{\omega ^21}}){\displaystyle \frac{a}{\eta }}{\displaystyle \frac{1}{a}}\mathrm{ln}\eta ,`$   (47)
where as usual, $`\omega =1+2\eta `$. Solving for $`a`$, one finds

$`a{\displaystyle \frac{2}{es}}\mathrm{ln}(e+s).`$   (48)
Trivial algebra leads to an explicit though slightly messy expression for the function $`f`$ in the asymptotic relation $`\alpha \delta =f(\alpha \mathrm{\Delta },\alpha S)`$. Setting $`\delta =1`$ is equivalent to $`a=1`$, and with this constraint, (48) leads back to (3).

## 5 Logarithms in the perturbative regime

Logarithmic scaling violations are a characteristic feature of perturbative gauge theory in four dimensions, observed, for instance, for gauge theory operators of large dimension but low “twist”—where twist is dimension minus spin. Their anomalous dimensions are responsible for violations of the Bjorken scaling in deep inelastic scattering . As an example, consider the operator

$$𝒪_{\mu _1\mathrm{}\mu _n}^\varphi =\varphi ^{}_{(\mu _1}\mathrm{}_{\mu _n)|}\varphi ,$$
(49)
for a gauge theory with some scalar fields transforming in a given representation (which we shall eventually specialize to the adjoint, as appropriate to $`𝒩=4`$ supersymmetric Yang-Mills theory). The symmetrization $`(\mathrm{})|`$ denotes also a removal of traces. We restrict to even $`n`$ since this is the only non-zero case for $`𝒩=4`$ SYM. The gauge-covariant derivative is $`_\mu =_\mu +ig_{YM}A_\mu `$. In the following calculation, we will not attempt to construct conformal primaries—so in principle there can be mixing between the operators we consider and others of twist two. Nor will we try to write down the one-loop amplitudes with all factors and signs precise: the main point will be to remind the reader of why the dominant one-loop effects grow logarithmically with $`n`$. In the free theory, the operator $`𝒪^\varphi `$ has dimension $`n+2`$ and spin $`n`$, hence twist $`2`$. We would like to inquire what anomalous dimension arises at one loop. This is closely analogous to a classic perturbative QCD calculation . The dominant graph has two scalars and a gauge boson coming out of the vertex, and the gauge boson rejoining one scalar line. It is convenient to introduce

$$𝒪_\mathrm{\Delta }^\varphi =𝒪_{\mu _1\mathrm{}\mu _n}^\varphi \mathrm{\Delta }^{\mu _1}\mathrm{}\mathrm{\Delta }^{\mu _n}$$
(50)
for any vector $`\mathrm{\Delta }^\mu `$. The anomalous dimension can be read off from the logarithmic term in the amplitude for the dominant graph:

$$=ig_{YM}^2C_2(R)\frac{d^4p}{(2\pi )^4}\frac{1}{p^2(pk)^2}\underset{j=0}{\overset{n1}{}}(\mathrm{\Delta }p)^j(\mathrm{\Delta }k)^{nj}=c_\varphi (\mathrm{\Delta }k)^n\mathrm{ln}\mathrm{\Lambda }^2+\mathrm{},$$
(51)
where $`C_2(R)`$ is the Casimir of the representation in which $`\varphi `$ falls. The $`j^{\mathrm{th}}`$ term in the sum comes from the term

$$ig_{YM}\varphi ^{}(_{\mu _1}\mathrm{}_{\mu _j}A_{\mu _{j+1}})_{\mu _{j+2}}\mathrm{}_{\mu _n}\varphi $$
(52)
in $`𝒪_{\mu _1\mathrm{}\mu _n}^\varphi `$. We still intend the traceless symmetrization of $`\mu _1\mathrm{}\mu _n`$, though it is no longer explicit in the notation. To kill off all contact terms and pick up only the logarithmic term that rescales $`𝒪_{\mu _1\mathrm{}\mu _n}^\varphi `$, we differentiate $`n`$ times with respect to $`k`$ and then set $`k=0`$:

$`ig_{YM}^2C_2(R){\displaystyle \frac{d^4p}{(2\pi )^4}\underset{j=0}{\overset{n1}{}}\left(\genfrac{}{}{0pt}{}{n}{j}\right)\frac{2^jj!}{p^{2j+4}}p_{\mu _1}\mathrm{}p_{\mu _j}(\mathrm{\Delta }p)^j(nj)!\mathrm{\Delta }_{\mu _{j+1}}\mathrm{}\mathrm{\Delta }_{\mu _n}}`$  $`=c_\varphi n!\mathrm{\Delta }_{\mu _1}\mathrm{}\mathrm{\Delta }_{\mu _n}\mathrm{ln}\mathrm{\Lambda }^2.`$   (53)
The integral diverges logarithmically. Replacing $`_0^{\mathrm{}}\frac{dp}{p}`$ by $`\mathrm{ln}\mathrm{\Lambda }`$, we wind up with

$$\frac{ig_{YM}^2C_2(R)}{16\pi ^2}\frac{1}{2\pi ^2}_{S^3}d^3\mathrm{\Omega }\underset{j=0}{\overset{n1}{}}2^j\widehat{p}_{\mu _1}\mathrm{}\widehat{p}_{\mu _j}(\mathrm{\Delta }\widehat{p})^j\mathrm{\Delta }_{\mu _{j+1}}\mathrm{}\mathrm{\Delta }_{\mu _n}=c_\varphi \mathrm{\Delta }_{\mu _1}\mathrm{}\mathrm{\Delta }_{\mu _n},$$
(54)
where $`\widehat{p}_\mu `$ is a unit vector in the unit three sphere, $`S^3`$, in Euclidean momentum space. The removal of trace terms can be accomplished, heuristically, by taking $`\mathrm{\Delta }_\mu `$ to be null. The angular averaging over $`S^3`$ that is left is a type of integral explained in . The result of doing this integral is

$$\frac{ig_{YM}^2C_2(R)}{16\pi ^2}\underset{j=0}{\overset{n1}{}}\frac{2^jj!}{(2j+2)!!}\mathrm{\Delta }_{\mu _1}\mathrm{}\mathrm{\Delta }_{\mu _n}=c_\varphi \mathrm{\Delta }_{\mu _1}\mathrm{}\mathrm{\Delta }_{\mu _n},$$
(55)
where $`n!!=_{j=0}^{n/2}(n2j)`$. Simplifying, we obtain

$$c_\varphi =\frac{ig_{YM}^2C_2(R)}{32\pi ^2}\underset{j=1}{\overset{n}{}}\frac{1}{j}\frac{ig_{YM}^2C_2(R)}{32\pi ^2}\mathrm{ln}n$$
(56)
for large $`n`$. This shows that the wavefunction renormalization, and hence the anomalous dimension, do scale as $`\lambda \mathrm{ln}n`$ for large $`n`$, as desired.444We thank T. Petkou for pointing out to us that a similar result has been obtained in . Calculations of this sort serve as classic demonstrations of logarithmic scaling violation in deep inelastic scattering. It is fascinating to see logarithms also in the supergravity dual, which is far from the perturbative regime! Of course, here the scaling is $`\sqrt{\lambda }\mathrm{ln}n`$. The turnover from $`O(\lambda )`$ to $`O(\sqrt{\lambda })`$ behavior is reminiscent of the coefficient for Wilson loops . For consistency with our supergravity result, the $`k`$-loop correction to the anomalous dimension should grow for large $`S`$ as $`\lambda ^k\mathrm{ln}S`$. This behavior is indeed observed in both supersymmetric and non-supersymmetric gauge theories . The successes  in computing circular Wilson loops to all orders in the ’t Hooft coupling lead us to hope that similar exact resummations (perhaps of rainbow graphs) might lead to a direct comparison between strongly coupled field theory and string theory near the leading edge of the Regge trajectory. This line of thought is particularly attractive in light of the fact that the states we are considering are nearly back-to-back Wilson loops—compare figure 1b) to 1c).

We should emphasize that the conclusion that in $`𝒩=4`$ SYM the $`k`$-loop correction to the anomalous dimension grows at most as $`\mathrm{ln}S`$ is highly non-trivial. In gauge theories individual graphs at $`k`$-loop order grow as fast as $`\lambda ^k(\mathrm{ln}S)^{2k1}`$ . Often there are cancellations, however.555We thank E. Witten for pointing this out to us. Analyses of the two-loop , and all higher order corrections  indeed indicate that the anomalous dimensions grow only as $`\mathrm{ln}S`$ perturbatively, and probably also non-perturbatively. Remarkably, there seems to be little difference in the behavior of these anomalous dimensions between the $`𝒩=4`$ SYM theory and QCD. This should have an interesting effect on the behavior of the deep inelastic scattering.

We should also note that there exist simple bilocal operators whose expansion generates all higher spin operators introduced above:

$`Tr\left\{\varphi ^{}(x)\mathrm{Pexp}(i{\displaystyle _x^y}A_\mu 𝑑x^\mu )\varphi (y)\mathrm{Pexp}(i{\displaystyle _x^y}A_\mu 𝑑x^\mu )\right\}`$  $`={\displaystyle \underset{n=0}{\overset{\mathrm{}}{}}}𝒪_{\mu _1\mathrm{}\mu _n}^\varphi (xy)^{\mu _1}\mathrm{}(xy)^{\mu _n}.`$   (57)
Thus, if the separation between $`x`$ and $`y`$ is taken to be light-like then expanding in powers of $`(xy)^\mu `$ we recover precisely the higher spin operators made out of two scalar fields and some number of covariant derivatives that we have been studying. Similar bilocal operators can be made by replacing $`\varphi `$ by a fermion field or $`F_{\mu \nu }`$. The growth of the anomalous dimensions with $`S`$ is clearly related to the presence of the path-ordered exponentials in (57), . It is also tempting to think that the “folded string” nature of the bilocal operators is related to the spinning string picture of the dual states in AdS5.

## 6 Discussion

Our discussion of spinning string solitons has so far been phrased in terms of the global AdS5 metric of Lorentzian signature. If we continue to Euclidean signature, both in spacetime and on the world sheet, then what we have done can be rephrased in terms of the Euclidean $`AdS_5`$ space written in Poincaré coordinates.

Introducing coordinate $`r=\mathrm{sinh}\rho `$ in (2), we may write the Euclidean continuation of the metric as

$$ds^2=(1+r^2)dt^2+\frac{dr^2}{1+r^2}+r^2d\mathrm{\Omega }_3^2.$$
(58)
This may be brought to the form

$$ds^2=d\phi ^2+e^{2\phi }\underset{i=1}{\overset{4}{}}dx_i^2=d\phi ^2+e^{2\phi }(dy^2+y^2d\mathrm{\Omega }_3^2)$$
(59)
by the coordinate change

$$\phi =t+\frac{1}{2}\mathrm{ln}(1+r^2),y=\frac{r}{\sqrt{1+r^2}}e^t.$$
(60)
Now we may substitute the Euclidean continuation of the spinning string soliton studied in section 3 to derive a soliton in Poincaré coordinates.

It is of further interest to consider more general metrics of the form

$$ds^2=d\phi ^2+a^2(\phi )\underset{i=1}{\overset{4}{}}dx_i^2.$$
(61)
which are relevant to more general gauge theories. In this case finding a spinning string soliton solution in closed form is less straightforward. If we attempt to transform to $`S^3`$ slicing of the geometry, then we generally arrive at a time-dependent metric of the form

$$f(r,t)dt^2+g(r,t)dr^2+r^2d\mathrm{\Omega }_3^2.$$
(62)
The time-dependence in these coordinates is a sign of broken conformal invariance. Suppose, however, that in the UV (for large $`\phi `$) the metric is asymptotic to AdS5: $`a(\phi )e^\phi `$. Then in the $`S^3`$ slicing of the geometry the metric approaches (58) for large $`r`$. For a spinning string with very large spin $`S`$, the dominant contributions to conformal dimension and spin arise from this large $`r`$ region where the metric is approximately AdS5. We conclude, therefore, that the relation (3) applies in the limit of large $`S`$ for all gauge theories that approach the $`𝒩=4`$ SYM theory asymptotically in the UV. We hope to return to construction and study of solitons in theories with different UV asymptotics in a future publication.

In this paper we have shown that some characteristically stringy effects can be extracted from the AdS/CFT duality by studying states whose Lorentz spin $`S`$ is much greater than $`R^2/\alpha ^{}=\sqrt{\lambda }`$. The dual description of gauge theory operators with such large $`S`$ cannot be given in terms of local fields in AdS5; instead it involves strings stretched across AdS5 in such a way that they probe the metric near its boundary. Our results are reliable for $`R^2/\alpha ^{}1`$, but one could hope that they are applicable qualitatively even for $`R^2/\alpha ^{}`$ of order 1.

In fact, recently there appeared interesting ideas on how to extend the AdS/CFT duality to large $`N`$ gauge theory at weak ‘t Hooft coupling $`\lambda `$ . In this case the relation between $`R^2/\alpha ^{}`$ and $`\lambda `$ is not known precisely. Naively, $`R^2/\alpha ^{}`$ is of order $`\lambda `$ in the weak coupling limit, but it is also possible that it approaches a number of order $`1`$ (there might not be an unambiguous definition of $`R`$ when it becomes as small as $`\sqrt{\alpha ^{}}`$). If we suppose that our results may be extrapolated to this situation, then the dual description of states with $`S1`$ is not in terms of local fields in $`AdS_5`$ but rather in terms of non-local stretched string states. This comment could be relevant to the search for infinite number of higher spin symmetries at $`\lambda =0`$ because the gauge theory operators we are discussing are precisely the higher spin currents.

Our results suggest that extra conservation laws, obvious at $`\lambda =0`$, persist at non-zero coupling in some asymptotic sense. Since we have $`(\mathrm{\Delta }S)/S1`$ for operators on the leading Regge trajectory, we find that the spacing of dimensions of these operators is asymptotically integral. These facts are not enough to predict an exact conservation law, as one may be able to do if $`\mathrm{\Delta }=S+2`$. But they are suggestive of asymptotic conservation laws as $`S`$ tends to $`\mathrm{}`$.

## Acknowledgments

We are very grateful to J. Maldacena for collaboration at early stages of this project. We also thank B. Altshuler, M. Bertolini, K. Efetov, G. Korchemsky, P. Ouyang and E. Witten for useful discussions. The work of SSG is supported in part by DOE grant DE-FG02-91ER40671 and an Outstanding Junior Investigator award. The work of IRK and AMP is supported in part by the NSF Grant PHY-9802484.


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# NUCLEAR SPIN CONVERSION IN POLYATOMIC MOLECULES

## 1 INTRODUCTION

### 1.1 Hydrogen spin isomers

At the beginning of the century physicists were puzzled by two seemingly unrelated phenomena: the anomalous specific heat of hydrogen discovered by Eucken in 1912  and the line intensity alternation in molecular spectra discovered by Mecke in 1925 . The solution of these two problems was a landmark in the foundation of quantum mechanics. As was pointed out by Farkas, “it was a real triumph for theory when in 1929 Bonhoeffer and Harteck  succeeded in bringing forward experimental evidence for the existence of the two different modifications of hydrogen” .

Three quarters of a century later, the explanation of these problems looks almost trivial. There are two nuclear spin isomers of H2 which differ by total spin ($`I`$) of the two hydrogen nuclei: $`I=1`$ for ortho hydrogen and $`I=0`$ for para hydrogen. The symmetry of the molecular wave function upon interchange of the two protons allows only odd values of rotational angular momentum ($`J`$) for ortho and only even values of $`J`$ for para. The spin isomers of H2 are extremely stable, having a conversion time on the order of 1 year at room temperature and 1 atm for pure hydrogen .

It is useful to recall the principle of the hydrogen spin isomer separation. A unique property of hydrogen molecules is their anomalously big rotational level spacing. The energy gap between the $`J`$=0 and $`J`$=1 states (first para and ortho states of hydrogen, respectively) is $`170`$ K. This energy gap is much larger than the boiling point of liquid hydrogen (20.4 K). The standard method of hydrogen isomer separation consists of cooling down the gas to 20.4 K in the presence of a catalyst (like activated charcoal or Fe(OH)3) which speeds up the equilibration. After equilibrium is reached, 99.8% of the hydrogen molecules are in the lowest rotational state $`J`$=0 which is the para state. After warming up the gas, one has pure para hydrogen at ambient temperatures because of extremely slow ortho-para conversion.

The discovery of hydrogen spin isomers triggered extensive investigations into their physical, chemical and even biological properties. Contrary to the intuitive feeling that nuclear spins are “deeply hidden” inside the molecule and cannot be important in practice, they play a decisive role in some practical problems. The most famous example is the storage of liquid hydrogen, e.g., as a rocket fuel, where considerable boil-off is caused by the energy released from ortho-para conversion. Research on hydrogen spin isomers, over nearly 70 years, has been reviewed in a few monographs  and is not considered in this paper.

### 1.2 Other molecules

The study of molecular spin isomers gave the first experimental background for the concept of nuclear spin (see, e.g., ), finally establishing the general relation between spin and statistics of identical particles. For molecular physics this theorem has as a consequence that molecules having identical nuclei in symmetrical positions (e.g., H2, NH3, CH4, N2, etc.) occur in nature only in the form of nuclear spin isomers for which selection rules prescribe particular rotational quantum numbers to particular spin states.

Nuclear spin isomers of molecules other than hydrogen formed a long standing puzzle. Even 50 years after the discovery of hydrogen spin isomers one could safely state that “no one has ever produced gaseous samples of any molecules other than H2 or D2 in which the ratio of the concentrations of the different nuclear spin symmetry species is different from the high temperature equilibrium value” . Thus, on one hand, quantum mechanics predicted the existence of stable spin isomers (see, for example, , p. 426), and on the other hand, almost nothing was known about their stability and their properties, for lack of practical separation methods. The simple technique of hydrogen isomer separation obviously fails in the case of heavy molecules, which have much smaller rotational level splitting and a much higher boiling point. Consequently, at temperatures sufficiently low for isomer enrichment the gas becomes solid. Thus the separation of spin isomers of heavy molecules requires a special technique. This is a non-trivial problem because spin isomers have identical masses and quite similar physical and chemical properties. Nevertheless, separation methods are under development now. In this Section we briefly review these methods.

$``$ Low-temperature solids. Small molecules embedded in special matrices partially retain their spin isomer features. This allows one to produce in solids at low temperature significant enrichment of spin isomers in comparison with their abundance at room temperature. One may hope that the enrichment will be retained after fast evaporation of these molecules into the gas phase. In paper  an attempt was made to separate spin isomers of methane using rapid heating of a solid held at low temperature. In a subsequent paper  (see also ), these authors attributed the negative result of  to fast conversion due to the degeneracy of methane states having different spin symmetry. Yet this issue deserves further investigation because fast (although in a different time range) cooling of methane in a molecular jet is not accompanied by spin conversion .

$``$ Selective photolysis. Due to the difference in allowed rotational quantum numbers, different spin isomers are spectroscopically distinguishable. (In fact, this is the essence of the famous line intensity alternation effect). In the enrichment method proposed in  narrow band laser radiation destroys one of the spin isomers from an equilibrium mixture by photolysis. This method was first applied to the enrichment of I2 spin isomers . It is not certain yet if I2 can be enriched by selective photolysis because the results  could not be reproduced in .

Selective photolysis was used for enrichment of spin isomers of formaldehyde (CH2O) molecules in . The authors obtained enriched hydrogen (one of the photolysis products), but enrichment of CH2O was not achieved. The conclusion was that the spin conversion is too fast in comparison with the duration of the photolysis . Later, with an improved setup, enrichment of CH2O spin isomers by selective photolysis was nevertheless demonstrated . Those authors measured the life time of the formaldehyde spin isomers to be 200 sec. As a possible mechanism of conversion the authors  proposed the mixing of states model .

$``$ Exchange reactions. Another approach to the separation of spin isomers of heavy molecules is based on the use of chemical exchange reactions with spin-polarized atoms. This technique proved feasible for the enrichment of nuclear spin isomers of diatomic molecules in  where enrichment of Na2 and Li2 was obtained.

$``$ Selective adsorption/condensation. The difference in rotational quantum numbers for different spin isomers can cause a difference in their physical properties, e.g., in adsorption on surfaces. This can be used for separation. Thus spin isomers of water molecules were separated by selective condensation  and by selective adsorption on Al2O3 surface . This group measured the life time of water spin isomers to be $`4.4\pm 0.2`$ days. Presumably, the isomers convert on the container surface . No model was proposed so far for the conversion of water.

$``$ Chemical reactions. The dependence of chemical reactions on the nuclear spin state of the reacting molecules was predicted in . This selectivity was employed in experiment  to obtain enriched samples of H$`{}_{}{}^{+}{}_{3}{}^{}`$ molecules by chemical reactions involving enriched H2.

$``$ Light-induced drift. A breakthrough in the separation of spin isomers was achieved in Ref.  by using Light-Induced Drift (LID) . CH3F isomer separation was analogous to the previously performed enrichment of the CH3F isotope species (see  and references therein). The LID effect proved to be a convenient tool since it enables one to separate spin isomers in the gas phase at well-defined gas composition, temperature and pressure. Although this technique can be applied to any molecular species in principle, the first experiments were performed on CH3F for the following reasons. The two nuclear spin species, characterized by their total proton spin $`I`$=3/2 or 1/2, have well-distinguishable rovibrational absorption lines which are easily accessible by a CO2 laser. In addition, CH3F is chemically inactive and has low adsorption onto the cell walls. These fortunate circumstances have promoted substantial progress in the field. The first measurement of the life time of nuclear spin isomers of polyatomic molecules was performed for 12CH3F and gave 2 hours . In subsequent measurements  nearly two orders of magnitude difference in the conversion rates of spin isomers of 13CH3F and 12CH3F molecules was observed.

At the time of these experiments the nuclear spin conversion of CH3F molecules was considered to be a heterogeneous process. The situation changed when it was proven  that the CH3F conversion is a gaseous process having an anomalously large isotope dependence $`(14\pm 1)\times 10^3`$ s-1/torr for the 13CH3F isomers and $`(0.31\pm 0.03)\times 10^3`$ s-1/torr for the 12CH3F isomers. Although these rates are extremely fast if compared to the H2 case, they are astonishingly slow if considered from a gas-kinetic point of view: the molecules retain their spin state even after suffering some 109 collisions which totally scramble the rotational state. The first feeling of a researcher in this situation is that the phenomenon is too complicated to expect a simple description based on first principles. Nevertheless, there is such simple model as will be shown below.

## 2 THEORY

### 2.1 Quantum relaxation

An explanation of the CH3F spin conversion was suggested  in the framework of a model based on intramolecular mixing of ortho and para states of the molecule. This model was proposed in a theoretical paper by Curl et al  as a tentative mechanism of spin conversion in H2O, CH2O and CH4. The model  formed the basis of a new approach to the spin conversion in polyatomic molecules.

The essence of spin conversion induced by intramolecular mixing consists of the following. Let us divide the quantum states of a molecule into two subspaces, ortho and para, each having their own rotational energy levels. This is symbolized in Figure 1. Let us assume for simplicity that only one pair of ortho and para states ($`m`$-$`n`$) is mixed by an intramolecular perturbation. Suppose that at the beginning of the conversion process a test molecule is placed in the ortho subspace. Collisions of the test molecule with the surrounding particles cause fast migration inside the ortho subspace but cannot, by assumption, change its spin state directly. This running up and down along the ladder of ortho states continues until the molecule arrives in the state $`m`$ which is mixed with the energetically close para state $`n`$. During the free flight after this collision, the para state $`n`$ will be admixed by the internal perturbation to the ortho state $`m`$, which creates a coherent mixture of the $`m`$ and $`n`$ states. The next collision can destroy this coherent mixture of states by transferring the molecule to other para states. This will localize the molecule inside the para subspace, and conversion has taken place.

To summarize, the mechanism of spin conversion is based on intramolecular mixing of ortho and para states and collisional destruction of the coherence between the states. This type of relaxation deserves a special name and can be called “quantum relaxation” . Processes of similar origin are well known in various parts of physics. First of all we can mention the relaxation of magnetic polarization in NMR . Another example is the vibrational energy transfer enhanced by Coriolis perturbation (see  and references therein). The same mechanism is responsible for the singlet-triplet relaxation in spin-radical pairs . Analogous mechanisms can be found also in elementary particle physics, e.g., neutral kaon decay .

Below we give a rigorous model of isomer conversion by quantum relaxation , hoping that the reader will enjoy seeing how a few steps of simple mathematics bring us to a general solution of a complicated problem. Suppose, that the molecular Hamiltonian is the sum of the two parts

$$\widehat{H}=\widehat{H}_0+\mathrm{}\widehat{V},$$
(1)
where $`\widehat{H}_0`$ is the main part of the Hamiltonian which has pure ortho and para states as the eigen states; $`\widehat{V}`$ is a small intramolecular perturbation which mixes the ortho and para states.

The Liouville equation for the density matrix $`\rho `$ of the molecule in the representation of the eigen states of the operator $`\widehat{H}_0`$ reads

$$(/t)\rho _{\alpha \alpha _1}=S_{\alpha \alpha _1}i[\widehat{V},\rho ]_{\alpha \alpha _1},$$
(2)
where $`S_{\alpha \alpha _1}`$ is the collision integral and $`\alpha `$ and $`\alpha _1`$ represent the complete sets of quantum states.

Using Eq.(2) one can obtain an equation which governs the change of molecular concentration in one particular nuclear spin state. This can be done by calculating the trace of Eq.(2) over all states of one spin isomer. For example, for the concentration of ortho molecules ($`\rho _o`$) one has

$$(/t)\rho _o=2Re\underset{\alpha o,\alpha ^{}p}{}i\rho _{\alpha \alpha ^{}}V_{\alpha ^{}\alpha };\rho _o\underset{\alpha o}{}\rho _{\alpha \alpha },$$
(3)
where $`\alpha `$ runs over all ortho ($`o`$) states and $`\alpha ^{}`$ runs over all para ($`p`$) states. Henceforth, unprimed quantum numbers will refer to the ortho states, and the primed ones to the para states.

When deriving Eq.(3) we have assumed that collisions conserve the number of molecules in each spin state (no “direct” conversion). This can be expressed as

$$\underset{\alpha o}{}S_{\alpha \alpha }=\underset{\alpha ^{}p}{}S_{\alpha ^{}\alpha ^{}}=0.$$
(4)
This property means that the collisional cross-section of ortho-para transfer is equal to zero: $`\sigma (p|o)`$=0. The justification of the relations (4) for CH3F molecules, both experimental and theoretical, can be found in .

To find the time dependence of $`\rho _o`$ from Eq.(3) we need to know the off-diagonal matrix elements of $`\rho `$, which are a measure of the coherence between ortho and para states. From Eq.(2) we have

$$(/t)\rho _{\alpha \alpha ^{}}=S_{\alpha \alpha ^{}}i[\widehat{V},\rho ]_{\alpha \alpha ^{}}.$$
(5)
In first order perturbation theory, on the right hand side of Eq.(5) one has to keep only the unperturbed values of the density matrix. Those are the diagonal matrix elements of $`\rho `$. This leads to the equation

$$(/t)\rho _{\alpha \alpha ^{}}=S_{\alpha \alpha ^{}}iV_{\alpha \alpha ^{}}(\rho _{\alpha ^{}\alpha ^{}}\rho _{\alpha \alpha }).$$
(6)
Here we have assumed that perturbation $`\widehat{V}`$ has no diagonal matrix elements. Such definition of $`\widehat{V}`$ is always possible by proper separation (1) of the molecular Hamiltonian.

Further, we will model the off-diagonal elements of the collision integral solely by a decay process: $`S_{\alpha \alpha ^{}}=\mathrm{\Gamma }_{\alpha \alpha ^{}}\rho _{\alpha \alpha ^{}}`$. The decoherence rate $`\mathrm{\Gamma }_{\alpha \alpha ^{}}`$ is approximately equal to the average of the population decay rates in the states $`\alpha `$ and $`\alpha ^{}`$. Note that $`\mathrm{\Gamma }_{\alpha \alpha ^{}}`$ is proportional to the gas pressure. Moreover, we assume all $`\mathrm{\Gamma }_{\alpha \alpha ^{}}`$ to be equal: $`\mathrm{\Gamma }_{\alpha \alpha ^{}}\mathrm{\Gamma }`$. Thus the off-diagonal terms of the collision integral will be modeled by the Anzatz

$$S_{\alpha \alpha ^{}}=\mathrm{\Gamma }\rho _{\alpha \alpha ^{}}.$$
(7)
The validity of this model will be tested below by comparison with experiment.

The intramolecular perturbation $`\widehat{V}`$ is time independent. Consequently, the time dependence of $`V_{\alpha \alpha ^{}}`$ is given by $`\mathrm{exp}(i\omega _{\alpha \alpha ^{}}t)`$ where $`\mathrm{}\omega _{\alpha \alpha ^{}}`$ is the energy gap between the states $`\alpha `$ and $`\alpha ^{}`$. Using the assumptions made above, the steady-state solution of Eq.(6) reads

$$\rho _{\alpha \alpha ^{}}=\frac{iV_{\alpha \alpha ^{}}}{\mathrm{\Gamma }+i\omega _{\alpha \alpha ^{}}}(\rho _{\alpha ^{}\alpha ^{}}\rho _{\alpha \alpha }).$$
(8)
Combining (3) and (8) one has

$$\frac{\rho _o}{t}=\underset{\alpha o,\alpha ^{}p}{}\frac{2\mathrm{\Gamma }V_{\alpha \alpha ^{}}^2}{\mathrm{\Gamma }^2+\omega _{\alpha \alpha ^{}}^2}(\rho _{\alpha ^{}\alpha ^{}}\rho _{\alpha \alpha }).$$
(9)
The diagonal elements of the density matrix (which are populations of states) are determined by the Boltzmann distribution, $`W_\alpha `$, for ortho and para isomers independently:

$$\rho _{\alpha \alpha }=\rho _oW_\alpha ;\rho _{\alpha ^{}\alpha ^{}}=\rho _pW_\alpha ^{},$$
(10)
because the rotational relaxation inside the ortho and para subspaces is many orders of magnitude faster than the ortho-para conversion. In Eq.(10) $`\rho _o`$ and $`\rho _p`$ are the total concentrations of ortho and para molecules, respectively. The Boltzmann factors are determined in the standard way by the expression

$$W_\alpha =Z_{ortho}^1\mathrm{exp}(E_\alpha /kT),$$
(11)
for the ortho molecules and similarly for para. In (11), $`E_\alpha `$ is the energy of state $`\alpha `$; $`Z_{ortho}`$ and $`Z_{para}`$ are the partition functions for ortho and para molecules, respectively.

Let us represent $`\rho _o`$ as the sum of a steady-state and a time-dependent part: $`\rho _o=\overline{\rho }_o+\delta \rho _o(t)`$. By taking into account that the total molecular concentration $`N=\rho _o+\rho _p`$ is conserved, one finds from (9) and (10) an exponential decay:

$$\delta \rho _o(t)=\delta \rho _o(0)e^{\gamma t},$$
(12)
with the conversion rate

$$\gamma =\underset{\alpha o,\alpha ^{}p}{}\frac{2\mathrm{\Gamma }V_{\alpha \alpha ^{}}^2}{\mathrm{\Gamma }^2+\omega _{\alpha \alpha ^{}}^2}\left(W_\alpha ^{}+W_\alpha \right).$$
(13)
This expression gives the solution to the problem in first order perturbation theory. It is valid for not too strong mixing, such that

$$V^2\frac{\nu _{rot}}{4\mathrm{\Gamma }}\mathrm{max}\{\mathrm{\Gamma }^2,\omega ^2\},$$
(14)
where $`\nu _{rot}`$ is the rotational relaxation rate. Conversion in the more general case is considered in .

### 2.2 Ortho-para state mixing in CH3F

The model of spin conversion described above is simple and clear, but is there something inside a symmetrical molecule which mixes the ortho and para states? We know now that such mixing can be produced by hyperfine interactions. These interactions are very weak and usually show up as small effects on a much larger background. Quantum relaxation of spin isomers provides an example of a phenomenon for which hyperfine interactions are the leading force.

Hyperfine interactions in molecules are important for various physical problems, first of all for hyperfine spectroscopy. We note that for the nuclear spin conversion one needs a specific part of hyperfine interaction which mixes the ortho and para states. This part of hyperfine interaction is unimportant for standard hyperfine spectroscopy but is important for level crossing/anticrossing spectroscopy (see Ref.  and references therein).

Let us recall the classification of CH3F quantum states. As a consequence of the CH3F symmetry the molecules exist in form of two nuclear spin isomers: ortho and para which have a total spin of three hydrogen nuclei $`I=3/2`$ and $`I=1/2`$, respectively (see, for example ). The ortho molecules have $`K`$-values ($`K`$ refers to the angular momentum projection on the molecular symmetry axis) divisible by 3: $`K=0,3,6\mathrm{}`$. For para isomers only $`K=1,2,4,5\mathrm{}`$ are allowed. Consequently, the quantum states of CH3F are divided into two subspaces, ortho and para, which are shown in Figure 1 for the particular case of 13CH3F molecules.

An analysis of ortho-para mixing in CH3F in relation with the spin conversion problem was performed in a few papers. Two sources of mixing in CH3F have been considered so far: spin-spin interactions between the molecular nuclei  and spin-rotation interactions .

Spin-spin interactions. The ortho and para states in CH3F are mixed by spin-spin interaction between the three hydrogen nuclei ($`\widehat{V}_{HH}`$), the fluorine–hydrogen nuclei ($`\widehat{V}_{FH}`$) and the carbon–hydrogen nuclei ($`\widehat{V}_{CH}`$) in the case of 13CH3F (see Figure 2). These interactions can be written as

$`\widehat{V}_{HH}`$ $`=`$ $`P_{HH}{\displaystyle \underset{m<n}{}}\widehat{𝐈}^{(m)}\widehat{𝐈}^{(n)}{}_{}{}^{}𝐓_{}^{(m,n)};\widehat{V}_{FH}=P_{FH}{\displaystyle \underset{m}{}}\widehat{𝐈}^{(m)}\widehat{𝐈}^F{}_{}{}^{}𝐓_{}^{mF};`$
$`\widehat{V}_{CH}`$ $`=`$ $`P_{CH}{\displaystyle \underset{m}{}}\widehat{𝐈}^{(m)}\widehat{𝐈}^C{}_{}{}^{}𝐓_{}^{mC},`$ (15)
with $`m,n=1,2,3`$ denoting the protons. In (15) $`P`$ are scale factors having the order of magnitude $`10^4`$ Hz. Their numerical values are given in ; $`\widehat{𝐈}`$ are the spin operators of the corresponding nuclei; $`𝐓`$ are the second rank tensors for the magnetic dipole–dipole interaction having the form, e.g.,

$$T_{ij}^{mF}=\delta _{ij}3n_i^{mF}n_j^{mF},$$
(16)
where $`𝐧^{mF}`$ is the unit vector directed from the H(m) to the F nucleus.

The spin conversion rate in 13CH3F molecules induced by the spin–spin interactions $`\widehat{V}^{SS}=\widehat{V}_{HH}+\widehat{V}_{FH}+\widehat{V}_{CH}`$, is given by the expression (13) having a mixing efficiency for the ortho-para level pair ($`J^{}`$,$`K^{}`$)-($`J`$,$`K`$)

$`{\displaystyle V_{\alpha \alpha ^{}}^{SS}^2}`$ $``$ $`F_{SS}(J^{},K^{}|J,K)=(2J^{}+1)(2J+1)\left(\begin{array}{ccc}\hfill J^{}& 2& \hfill J\\ \hfill K^{}& q& \hfill K\end{array}\right)^2\times `$ (20)
$`\left(3P_{HH}𝒯_{2q}^{(1,2)}^2+2P_{FH}𝒯_{2q}^{1F}^2+2P_{CH}𝒯_{2q}^{1C}^2\right).`$
Here $`𝒯`$ are the spherical components of the corresponding $`𝐓`$-tensors calculated in the molecular frame (for their numerical values see ); (: : :) stands for the 3-j symbol. In the left-hand side of (20) summation is performed over degenerate quantum numbers of the states $`\alpha `$ and $`\alpha ^{}`$ which are the projections on the laboratory quantization axis of molecular angular momentum $`M`$, spins $`\sigma `$, $`\sigma ^F`$, $`\sigma ^C`$ of the three protons, fluorine and carbon nucleus, respectively.

The selection rule for the spin-spin mixing follows from Eq.(20):

$$\mathrm{\Delta }J2;J^{}+J2;\mathrm{\Delta }K2.$$
(21)
Note that mixing of states having $`\mathrm{\Delta }K=0`$ does not contribute to the spin conversion. By contrast, the level shift in hyperfine spectroscopy is dominated by the diagonal matrix elements of $`\widehat{V}`$ having $`\mathrm{\Delta }K=0`$.

The spin-spin interaction in CH3F can be determined with rather high accuracy, limited presently to a few percent by the uncertainty in the molecular spatial structure. The most accurate data for the CH3F structure are given in Ref. .

Spin-rotation interaction. Another source of ortho-para mixing in CH3F is the spin-rotation coupling which results from the interaction of the nuclear spins with the magnetic field induced by molecular rotation . The spin-rotation perturbation relevant for the ortho-para mixing can be written as

$$\widehat{V}_{SR}=\frac{1}{2}\underset{n}{}[\widehat{𝐉}𝐂^{(n)}\widehat{𝐈}^{(n)}+H.C.],$$
(22)
where $`𝐂^{(n)}`$ is the spin-rotation tensor for the $`n`$-th hydrogen nucleus. The expression for the ortho-para mixing efficiency due to the spin-rotation interaction can be found in the original papers .

The selection rules for the spin-rotation interaction read

$$\mathrm{\Delta }J1;\mathrm{\Delta }K2.$$
(23)
As can be seen from the selection rules (21) and (23), there are ortho-para level pairs which are mixed exclusively by spin-spin but not by spin-rotation interaction, viz., $`\mathrm{\Delta }J=2`$. This can be used to disentangle the contribution to the spin conversion from these two mechanisms of state mixing .

In contrast to spin-spin interaction, the spin-rotation interaction in CH3F is known presently only approximately. It was proposed  to use nuclear spin conversion itself as a source of information on spin-rotation perturbation in molecules. Such information would be complementary to the information provided by standard hyperfine spectroscopy.

### 2.3 CH3F level structure and theoretical conversion rates

Spin conversion by quantum relaxation is dependent on the position of ortho and para states, notably the ortho-para level gaps. They are not accessible directly by standard spectroscopical methods. Nevertheless, if a complete set of molecular parameters is available one can calculate the positions of all states and thus the ortho-para level gaps. The accuracy of the molecular parameters should be rather high to guarantee the determination of the level position within $`110`$ MHz because only close ortho-para level pairs contribute substantially to the conversion. For CH3F such accurate parameters are available from high-resolution spectroscopy .

A search for close ortho-para level pairs in CH3F was performed in . At the time, a complete set of ground state molecular parameters was available for 12CH3F only . For 13CH3F the molecular parameters $`A_0`$ and $`D_0^K`$ were missing. Nevertheless, a search for close ortho-para level pairs was performed for both molecules using the estimation of $`A_0`$=5.18240(6) cm-1 made by T Egawa and K Kuchitsu (unpublished data) and assuming $`D_0^K`$ equal for both isotopes. This search revealed that only two ortho-para level pairs are important for the spin conversion in 13CH3F. For 12CH3F four important ortho-para level pairs were found. This choice of level pairs was confirmed and their energy gaps determined more precisely in  on the basis of new accurate molecular parameters determined in . The best presently available values for the CH3F ortho-para level gaps are given in Table 1.

In addition to the ortho-para level spacing, $`\omega _{\alpha \alpha ^{}}`$, and the efficiency of the ortho-para mixing, $`V_{\alpha \alpha ^{}}`$, the decoherence rate, $`\mathrm{\Gamma }`$, should be determined in order to calculate the conversion rates. This is a rather complicated problem that has not yet been resolved. Approximately, the rate $`\mathrm{\Gamma }`$ can be taken equal to the level population decay rate. Even so, the uncertainty remains because the population decay rates of the states important for the conversion (see Table 1) have not been measured. There is a measurement of the population decay rate in the state ($`J`$=4, $`K`$=3) of 13CH3F  which was determined to be 1$``$108 s-1/torr.

Since the decoherence rate $`\mathrm{\Gamma }`$ is close to but nevertheless different from the level population decay rate, it is more consistent to determine $`\mathrm{\Gamma }`$ from the nuclear spin conversion itself by fitting the measured conversion rate. Such an approach  yields $`\mathrm{\Gamma }1.8`$108 s-1/torr which is indeed close to the level population decay rate 1$``$108 s-1/torr . The various mixing processes in CH3F are illustrated in Table 1 where the contributions to the conversion are calculated assuming the decoherence decay rate $`\mathrm{\Gamma }=1.8`$108 s-1/torr for all pairs of ortho-para states in both molecules.

From the data in Table 1 one can see that the conversion in 12CH3F by spin-spin interaction is much slower than in 13CH3F. On the other hand, in 12CH3F the spin-rotation interaction was predicted to be the leading mechanism . The key point is the right choice of the decoherence rate $`\mathrm{\Gamma }`$ for the most important level pair in 12CH3F: (28,5)-(27,6). It was proposed in  to use $`\mathrm{\Gamma }210^7`$ s-1/torr for this pair in order to fit the experimental value for the rate.

## 3 EXPERIMENTAL METHOD

### 3.1 Spin isomer separation by LID

It is the introduction of the Light-Induced Drift (LID)  as a separation tool that has brought substantial progress in the field of nuclear spin isomers over the last decade. The essence of LID is explained in Figure 3. Let us consider a gas of two-level particles interacting with a traveling monochromatic wave. Due to the Doppler effect, the radiation will excite particles selectively with respect to their velocity component along the radiation k-vector.

Suppose that the absorbing particles are diluted in a buffer gas and that the laser frequency is chosen such that the radiation excites only molecules moving away from the laser. Because the excited molecules have in general a different (usually bigger) kinetic cross section than the unexcited particles, the mean free path for molecules moving away from the laser will be different (usually smaller) than for molecules moving towards the laser. This difference in mean free path will create a drift of absorbing particles towards the laser. The buffer gas will flow in the opposite direction as required by momentum conservation. The direction of the fluxes depends on the sign of the laser frequency detuning from the absorption line center and the direction of the wave vector k. In a closed tube the LID effect results in a spatial separation of the two gas components, which can be quite substantial even if the fluxes themselves are relatively small.

A quantitative description of the LID effect in molecules is a complicated problem because LID depends on small difference in transport properties between excited and ground state molecules, which is rather difficult to calculate. A crucial parameter is the relative change in cross section, or – more precisely – in collision rate, $`\mathrm{\Delta }\nu /\nu `$, upon excitation. In general, $`\mathrm{\Delta }\nu /\nu `$ depends on velocity, and thus on the detuning. In some cases $`\mathrm{\Delta }\nu /\nu `$ can even change sign as a function of detuning, giving rise to so called “anomalous LID” (see, e.g., Refs. ). Here we will limit ourselves to the simplified case that $`\mathrm{\Delta }\nu /\nu `$ can be considered constant. In this case the description of LID is relatively simple  and yields for the difference in absorbing particle density between the ends of the tube

$$\mathrm{\Delta }n=\frac{\mathrm{\Delta }\nu }{\nu }\frac{2\mathrm{\Delta }S}{\mathrm{}\omega v_0}\phi (\mathrm{\Omega }),$$
(24)
where $`\mathrm{\Delta }S`$ is the absorbed laser intensity; $`\mathrm{}\omega `$ is the photon energy; $`v_0=\sqrt{2kT/m}`$ is the thermal speed; $`\phi (\mathrm{\Omega })`$ describes the behavior as a function of detuning, $`\mathrm{\Omega }=\omega \omega _0`$, of the laser frequency, $`\omega `$, from the absorption line center frequency, $`\omega _0`$. The spectral function $`\phi (\mathrm{\Omega })`$ can be readily calculated if the homogeneous line width of the absorbing transition is known. For small frequency detuning and low pressure, the function $`\phi (\mathrm{\Omega })v_L/v_0`$, where $`v_L=\mathrm{\Omega }/k`$ is the resonant velocity component of the absorbing particle along the $`𝐤`$-vector. Examples of $`\phi (\mathrm{\Omega })`$ for various homogeneous line widths, as well as corrections to (24) due to the finite gas dilution are given in .

It was shown in Ref.  that the LID effect in the CH3F isotope mixture, which should behave similar to the mixture of spin isomers, is consistent with the model of constant $`\mathrm{\Delta }\nu /\nu `$. The change in collision rate, $`\mathrm{\Delta }\nu /\nu `$, upon rovibrational excitation was found to be $``$1%. For more details on the LID effect see Ref.  and Refs. which review the LID effect in molecular gases.

A prerequisite of the LID separation of gas components is their spectral distinguishability. This is perfectly satisfied for CH3F for which ortho and para isomers are different by $`K`$ and thus have different absorption spectra. There are two convenient coincidences between absorption lines of 13CH3F and 12CH3F molecules in the $`\nu _3`$ fundamental band (C–F stretch) and CO2-laser lines , which were used for spin isomer separation. The absorption spectra of ortho and para 13CH3F near the P(32) line of the 9.6$`\mu `$ band of a CO2-laser are shown in Figure 4. As can be seen from these spectra, the CO2-laser frequency tuned to the center of the 9P(32) laser line excites ortho 13CH3F molecules in the blue wing of the R(4,3). This results in LID of ortho isomers towards the laser. In the case of 12CH3F, excitation of the molecular absorption line $`Q(12,2)`$ by the 9P(20) laser line induces a drift of para molecules away from the laser. In a typical experiment on CH3F spin isomer an enrichment of 10% was produced, sufficient to have good signal-to-noise ratio.

### 3.2 Relaxation time measurement

The experiments on CH3F were performed in Novosibirsk and Leiden using similar approaches. Separation of spin isomers was achieved in a long and thin glass tube using LID as outlined in Section 3.1. One end of the separation tube was connected with a test cell to collect an enriched gas sample. The other end of the separation tube was connected with a ballast volume, thus providing an equilibrium reference sample (see Figures 5 and 6). The degree of enrichment (or depletion, depending on the particular arrangement) was monitored by absorption, using a probe laser beam resonant with either the ortho, or the para isomer. To increase the sensitivity and stability of the detection system the absorption in the test cell was compared differentially with the absorption in a reference cell having equilibrium composition.

A schematic of the setup used in Ref.  is presented in Figure 5. The isomer separation was performed in a tube having length 1.5 m and inner diameter 1.3 mm by CO2-laser radiation (power $`10W`$). The radiation frequency was stabilized to the CO2 line center. For the enrichment detection, a small portion of the laser beam was directed through the test and reference cells which were placed on the same optical axis. The absorption in these cells was modulated in antiphase by external Stark electrodes. This modulation produced a component in the probe beam proportional to the absorption difference between the two cells. This differential signal was normalized by the signal proportional to probe beam intensity. The latter signal was created by additional Stark electrodes which modulated the absorption in the reference cell alone. The detection method used in  has a rather high sensitivity but has the drawback that it can be applied to molecules having permanent electric dipole moment only.

The setup used in Ref.  is presented in Figure 6. It has a separation tube of 30 cm length and 3 mm inner diameter for the study of 13CH3F. For 12CH3F a tube of 1 m length and 1.1 mm diameter was used to make up for the much smaller absorption of the $`Q(12,2)`$ transition used. In both cases the separation laser (a CO2 laser from Edinburgh Instrument, Model PL5) was frequency stabilized to the CO2-line center.

For the detection, a weak probe beam from an additional (waveguide) laser was used. Intensity and direction of the beam were stabilized using an Acousto Optic Modulator with a feed back loop and a set of diaphragms. The frequency was locked to the CH3F absorption line center using an additional absorption cell with CH3F gas at low pressure.

It is essential to be sure that the powerful CO2 laser radiation indeed produces separation of CH3F spin isomers and that spurious effects like gas heating, laser induced thermal diffusion, etc., do not contribute substantially to the signal. This important issue was addressed already in the first experiment, where the spin isomer separation was confirmed by comparing the optical signal with additional monitoring of the gas composition by a mass-spectrometer. A more decisive test was performed in  where it was demonstrated, by probing various ortho and para absorption lines, that the LID enrichment of ortho is accompanied by a corresponding depletion of para species. We stress that the conversion of spin isomers takes place in a part of the setup which is unaffected by the strong laser beam used for the isomer separation.

Depending on the problem at hand, the test cell could be connected to a Stark cell, or to a cell at elevated temperature, or to a cell containing different test surfaces. This allowed to study the influence of various physical factors on nuclear spin conversion.

The measurement procedure was generally as follows. First, the setup was filled with equilibrium gas and the detection system was set to zero absorption difference. Next, the enrichment was started by switching on the separation laser (first part of the curve in Figure 7). After a sufficient enrichment was achieved, the two probe cells were isolated by closing the appropriate valves and the conversion process began (the decay part in Figure 7). The measured decay curve was fitted by a function $`\mathrm{exp}(\gamma t)+\kappa t`$, where $`\gamma `$ is the conversion rate, while the second term accounts for a (small) drift of the detection signal.

## 4 EXPERIMENTAL RESULTS

### 4.1 Dependence on pressure and collision partner

In the following Sections we review the experiments which test the mechanism responsible for spin conversion in CH3F. Let us first consider the pressure dependence. The data for 13CH3F conversion in two buffer gases, 12CH3F and 13CH3F itself are shown in Figure 8. The rates have linear pressure dependence and are seen to be rather close. As the reference value we give the conversion in pure 13CH3F

$$\gamma _{13}/P=(12.2\pm 0.6)10^3s^1/torr,$$
(25)
where the subscript 13 refers to the isotopic species.

The linear pressure dependence of $`\gamma _{13}`$ is consistent with conversion by quantum relaxation. Indeed, at $`P`$1 torr the decoherence rate $`\mathrm{\Gamma }/2\pi 30`$ MHz, which is much smaller than the frequency gaps between the mixed states in 13CH3F (see Table 1). In this pressure limit, where $`\mathrm{\Gamma }\omega `$, one can neglect $`\mathrm{\Gamma }^2`$ in the denominator of Eq.(13) and the conversion rate becomes proportional to $`\mathrm{\Gamma }`$, thus proportional to pressure.

Note that the linear pressure dependence of $`\gamma _{13}`$ at low pressures in itself does not allow to distinguish between conversion by quantum relaxation and by ordinary gaseous relaxation. The latter would produce conversion with a rate $`2n\sigma (p|o)v`$ which is also linear in pressure (see Section 5.2). The important point is that quantum relaxation is able to reproduce the right order of magnitude for the conversion rate in 13CH3F . If one takes as an estimation for the decoherence rate $`\mathrm{\Gamma }=1`$108 s-1/torr, as follows from measurement , the spin-spin mixing of states in 13CH3F gives the conversion rate $`\gamma _{13}/P710^3`$ s-1/torr which is half the measured value.

Measurements of the 13CH3F spin conversion in various buffer gases are presented in Figure 9 . The conversion rates are rather close in buffer gas CH3Cl and in pure CH3F but are much smaller in buffer gases N2 and O2. As was concluded in , the buffer gas dependence of the conversion rate is in qualitative agreement with the buffer gas variation of the decoherence rate, $`\mathrm{\Gamma }`$, which was estimated in  on the basis of pressure broadening data. An important result of the data in Figure 9 is that the large magnetic moment of O2 ($`2\mu _B`$) seems to be unimportant the 13CH3F spin conversion. For more details on this point see Section 5.

### 4.2 Isotope effect

The measurements show a large isotope effect in CH3F conversion . In Figure 10 the 12CH3F conversion rate as a function of pressure is presented and seen to be much smaller than for 13CH3F (Figure 8). The ratio of the conversion rates in 13CH3F and 12CH3F measured in Leiden  was found to be

$$\gamma _{13}/\gamma _{12}=55\pm 4,$$
(26)
which is close to the value 46$`\pm `$5 measured in . The slow conversion rate in 12CH3F makes the measurements rather difficult to perform because of severe restrictions to the long term stability of the detection system.

The much smaller rate in 12CH3F results from the bigger gaps between the ortho and para states in this molecule in comparison with 13CH3F. There is one close pair of ortho-para states, viz., (51,4)-(50,6), but these states are situated at high energies and therefore hardly populated. The 13CH3F conversion is dominated by spin-spin mixing of the ortho and para states. In 12CH3F the spin-spin interaction gives only a small part of the observed rate . As was discussed in Section 2.3 and concluded in the papers  the conversion in 12CH3F is dominated by spin-rotation interaction.

### 4.3 Temperature dependence

The levels important for spin conversion in 13CH3F and 12CH3F are situated at widely different energies. Consequently, one would expect quite different temperature dependences of the rates in the two cases as the level populations will be affected differently by temperature. For example, the population of the states (11,1) and (9,3), which are dominant for 13CH3F conversion, will decrease at elevated temperature, in contrast with, e.g., states (51,4) and (50,6) of 12CH3F whose population will increase.

The temperature dependence of the conversion rate in the two molecules was reported in Ref. . The results of the measurements are presented in Figure 11. Indeed, the conversion rate in 12CH3F grows rapidly with increasing temperature. By contrast, the rate in 13CH3F decreases in the temperature range 300 - 600 K.

Presently we can propose only a rough model of the temperature dependence. The conversion rates is affected primarily through the Boltzmann occupation of rotational states. An additional temperature dependence may appear due to the temperature dependence of the decoherence rate $`\mathrm{\Gamma }`$. It proved sufficient to apply only a 25% temperature variation in $`\mathrm{\Gamma }`$ by the expression:

$$\mathrm{\Gamma }(T)=\left(1.8(TT_{room})1.510^3K^1\right)10^8s^1/torr,$$
(27)
to fit the experimental points for the 13CH3F conversion in the range from room temperature $`T_{room}`$=297 K up to 600 K, as shown by the thick line in Figure 11. Thus these data are qualitatively consistent with spin conversion by quantum relaxation (for $`T600`$ K see below).

The same temperature dependence of the decoherence rate $`\mathrm{\Gamma }(T)`$ was used to model the conversion in 12CH3F. Again, only spin-spin mixing of states was taken into account. The calculated rate in 12CH3F (thin line) reproduces the overall behavior but fails to reproduce the magnitude of the rate. This may not be surprising, since an additional contribution to the conversion rate in 12CH3F should result from spin-rotation interaction, as was pointed out in .

Above 600 K the conversion rate in 13CH3F increases again, which suggests an additional conversion mechanism at high temperatures. This mechanism seems to have no isotope selectivity, as one may conclude from Figure 11.

### 4.4 Level-crossing resonances

Eq.(13) predicts a strong dependence of the conversion rate on ortho-para level spacing at low pressures where $`\mathrm{\Gamma }\omega `$. To detect this effect, it was proposed  to split and cross the ortho and para levels of 13CH3F by a homogeneous electric field. This experiment was performed in  with the setup in Figure 6 equipped with an additional Stark cell.

Results of the measurement of the conversion rate in 13CH3F as a function of electric field are shown in Figure 12. As seen from these data the conversion rate is hardly affected by the field below 500 V/cm, but rises sharply above 600 V/cm.

A theoretical description of the level-crossing resonances presented in Figure 12 was developed in . A homogeneous electric field splits each state of CH3F into $`2J+1`$ magnetic sublevels due to the first order Stark effect. The energy gaps between the $`M`$-sublevels of the two states $`J^{},K^{},M^{}>`$ and $`J,K,M>`$ are given by the formula

$$\mathrm{}\omega _{M^{}M}()=\mathrm{}\omega _0d\left(\frac{M^{}K^{}}{J^{}(J^{}+1)}\frac{MK}{J(J+1)}\right),$$
(28)
where $`\mathrm{}\omega _0`$ is the energy gap between the states $`J^{},K^{}>`$ and $`J,K>`$ at zero electric field; $``$ is the electric field strength, $`d`$ is the molecular electric dipole moment. For 13CH3F, $`d`$ was taken to be 1.858 D (or $`6.198\times 10^{30}`$ C$``$m) .

In the model of level-crossing spectra  only spin-spin interaction was taken into account. In this case each ortho-para level pair gives the following “spectrum” of $`\gamma `$ as a function of field strength:

$$\gamma ()=\underset{Mo,M^{}p}{}\frac{2\mathrm{\Gamma }F_{SS}(J^{},K^{}|J,K)}{\mathrm{\Gamma }^2+\omega _{M^{}M}^2()}\left(\begin{array}{ccc}\hfill J^{}& J& 2\\ \hfill M^{}& M& M^{}M\end{array}\right)^2\left(W_\alpha ^{}+W_\alpha \right),$$
(29)
where $`F_{SS}(J^{},K^{}|J,K)`$ is the mixing efficiency from (20). The selection rule $`\mathrm{\Delta }M2`$ follows directly from (29). The only unknown parameter in expression (29) is the decoherence rate $`\mathrm{\Gamma }`$. This parameter was determined in  by fitting the experimental value of $`\gamma `$ in 13CH3F at zero electric field which gave $`\mathrm{\Gamma }1.810^8`$ s-1/torr.

Once $`\mathrm{\Gamma }`$ is determined, there are no free parameters in the model and the level-crossing spectra can be calculated. The result is presented in Figure 12. As can be seen from these data, the model reproduces the main features of the measured spectrum very well: positions of the peaks within a few MHz as well as their amplitude within 10%.

The spectrum in Figure 12 results from crossing of sublevels of the ortho state (9,3) and the para state (11,1). The level pair (21,1)-(20,3) gives a constant contribution to $`\gamma ()`$ in the electric field range of Figure 12 because of the much larger gap for this level pair: 350 MHz. The states (11,1) and (9,3) have $`\mathrm{\Delta }J=2`$ and consequently are mixed by spin-spin interactions but not by spin-rotation interaction. This justifies taking only spin-spin interaction into account in the modeling of the level-crossing resonances .

### 4.5 Quantum Zeno effect induced by collisions

In the high pressure limit, where $`\mathrm{\Gamma }\omega `$, one can neglect $`\omega `$ in the denominator of (13) and the conversion rate is seen to be inversely proportional to pressure (“$`1/P`$ dependence”). Consequently, at high pressures one has a very interesting regime of spin conversion in which rapid collisions prevent the molecule from changing its spin state: collisional inhibition of spin conversion. This slowing down of the conversion should start in the case of 13CH3F at pressures well above 10 torr. Unfortunately it was not possible to perform measurements at such high pressures because of a few experimental problems. First, the LID effect is reduced at high pressures due to loss of velocity selectivity by pressure broadening. Second, the attained level of enrichment at high pressures becomes smaller also because the diffusion-limited separation time increases whereas the spin relaxation time is rather short at 10 torr, making back-conversion during the enrichment stage more severe. Third, the sensitivity of the detection system decreases because of overlapping ortho and para absorption lines. Another approach to observe the slowing down of the conversion would be to enrich at low pressures and to increase the pressure afterwards. Such an attempt was unsuccessful mainly because of spurious effects accompanying the compression .

To overcome these problems one could, as an alternative, narrow the gap between the ortho and para levels by an external electric field. This would shift the slowing down of the conversion rate to lower pressures. The idea was realized in  by choosing the field strength at which the strongest peak in the spectrum of Figure 12 occurs. This peak is due to the crossing of sublevels $`M^{}`$=11 and $`M`$=9 at electric field 652.8 V/cm. If this resonant condition is chosen and the spin conversion is dominated by mixing of the resonant level pair, the description of the conversion is given by just one term from Eq.(29) which has $`\omega =0`$ in the denominator and gives a 1/P dependence.

The result of the measurements is shown in Figure 13. Indeed, there is a rapid slowing down of the conversion rate when the pressure increases from 0.05 torr to 0.5 torr. The plateau above 0.5 torr is the result of the neighboring $`M^{}M`$ level pairs which do not have zero gaps at the chosen electric field and, consequently, give a contribution which is still increasing with pressure. At still higher pressures, the conversion rate would go down again.

The experimental results in the high pressure range are in good agreement with the theory (solid line in Figure 13). The calculation of the pressure dependence was performed on the basis of Eq.(29) by taking into account all pairs ($`J^{}`$=11, $`K^{}`$=1, $`M^{}`$)-($`J`$=9, $`K`$=3, $`M`$); $`M^{}M2`$. The decoherence rate was taken to be $`\mathrm{\Gamma }`$=1.75x108 s-1/torr for all level pairs. Only the spin-spin mixing of states was taken into account because this pair of states has $`|\mathrm{\Delta }J|`$=2 and, consequently, is not mixed by the spin-rotation interaction, see (23).

At low pressure the theoretical conversion rates are systematically larger than the measured one. This can be attributed to the saturation effect which should occur at low pressure in case of degenerate ortho and para states when the first order perturbation theory breaks down

The inhibition of the conversion rate at increasing collision rate can be considered as an example of the Quantum Zeno effect . In the original version of this effect  the inhibition of the quantum system decay is due to frequent measurements which destroy quantum coherence by projecting the system to a particular quantum state. In our case the decoherence is produced by molecular collisions which destroy the coherence between the ortho and para states in the molecule.

## 5 DIRECT ORTHO-PARA TRANSITIONS IN CH3F

The investigation of nuclear spin conversion in CH3F would not be complete without studying direct ortho-para transitions in this molecule, i.e., transitions caused by the magnetic-field gradient from a collision partner or a surface. There is room for the conversion by quantum relaxation only if direct transitions are unimportant. Below we describe the two “direct” contributions to the conversion which are produced by surface or bulk collisions.

### 5.1 Direct conversion on surfaces

For the case of ortho and para H2, conversion on catalytic surfaces is by far the most efficient mechanism (see e.g. ). This may not be surprising in view of the extremely slow gas-phase conversion. But also for CH3F, conversion on surfaces plays a role. As was demonstrated in Refs., CH3F nuclear spin conversion can be quite different for different wall materials. The most rapid conversion (in fact instantaneous on the experimental time scale) was observed on Fe(OH)3 powder . The rate of conversion on this catalyst was limited, most likely, by diffusion.

Glass surfaces appeared to be rather inert for the CH3F conversion. The surface contribution to the conversion is given by a cutoff of the linear fit of the conversion rate vs. pressure. The data in Figure 8 determines the surface contribution on the order of 10-4 s-1. This yields a probability per collision for the molecule to convert $``$10-9 . There are other surfaces which do not seem to produce rapid conversion, e.g., aluminum and gold. On the other hand, conversion on the surface of magnetic tape was found to be rather fast .

### 5.2 Direct conversion by collisions

Another possible mechanism of direct ortho-para transitions is due to collisions in the bulk. In the case of hydrogen, it is known  that oxygen molecules speed up hydrogen conversion dramatically, although in a time domain different from the CH3F conversion. This phenomenon is well understood . The conversion is due to the steep magnetic field gradient produced by the collision partner.

Conservation of the nuclear spin symmetry of symmetric tops in molecular collisions was confirmed in a number of studies using various experimental approaches . This is not surprising, because we know now that spin isomers are very stable species.

Nevertheless, it would be useful to know the conversion rate in direct collisions. First of all we would like to stress that conservation of nuclear spin symmetry in molecular collisions is an approximate selection rule, although a very precise one. Like in the case of hydrogen, it can be violated if an inhomogeneous magnetic field is produced by a colliding molecule. From the measurements of the CH3F conversion rate one can estimate an upper bound for the cross section of direct spin-changing collisions $`\sigma (p|o)`$. Using the formula for the gas-kinetic relaxation rate $`\gamma _{coll}=2N\sigma (p|o)v`$ and the experimental value for the conversion rate 0.01 s-1  one obtains the estimation

$$\sigma (po)2.510^{24}cm^2.$$
(30)
Cross sections of this order are hardly accessible by conventional collision experiments, like molecular beams, or double resonance techniques.

In order to reveal the role of the magnetic moment of the collision partner, the 13CH3F spin conversion was studied in two buffer gases: N2 and O2 which have quite similar pressure broadening coefficients and, consequently, should have similar contributions to the conversion due to quantum relaxation . On the other hand, the magnetic moments of N2 and O2 are different by three order of magnitude, which can result in extra contribution to the conversion in the case of oxygen. From the data for 13CH3F presented in Figure 9, one can conclude that the role of the oxygen magnetic moment is too small to be visible on the much larger background which is due to conversion by quantum relaxation. Thus in order to observe direct ortho-para transitions one has to suppress the contribution by quantum relaxation. It was proposed in  to search for spin-violating collisions by studying spin conversion in 12CH3F, in which the conversion by quantum relaxation is slower by almost two orders of magnitude than in 13CH3F.

The results of the measurements are presented in Figure 14. One can see that the 12CH3F conversion is considerably faster in collisions with O2 than with N2. The difference in rates can be attributed  to direct ortho-para transitions. The estimation for the cross section from the data in Figure 14 reads

$$\sigma (p|o)=(6\pm 0.8)10^{26}cm^2.$$
(31)
We see from this result that even if CH3F is diluted in paramagnetic oxygen, the direct ortho-para transitions are very improbable if compared with ordinary kinetic cross sections. To understand to what extend the direct transition can influence the conversion in a “nonmagnetic” environment (like pure CH3F), one needs to scale the cross section $`\sigma (p|o)`$ for the various magnetic moments. Similar to the case of hydrogen , the cross section of direct transitions for CH3F scales with $`\mu ^2`$ where $`\mu `$ is the magnetic moment of the collision partner . Consequently, direct transitions can be neglected for CH3F spin conversion in a nonmagnetic environment.

## 6 CONCLUSION

It is well established by now that the nuclear spin isomers of molecules can be separated in the gas phase by using the Light-Induced Drift technique. The enriched gas samples can be stored in a separate test volume for further investigations of their properties.

In the present review we have used CH3F to investigate the mechanism behind nuclear-spin conversion. This molecule was found to have conversion rates in a convenient time domain, and turned out to be very versatile for investigating various aspects of the conversion process. The conversion was studied at various pressures, temperatures and gas compositions and for two isotopic species. The experimental results obtained for the CH3F spin isomers revealed that the conversion in the bulk is governed by a specific process which can be called quantum relaxation. This mechanism is based on the intramolecular mixing of molecular quantum states and collisional destruction of the quantum coherence between the mixed states.

Various key points in the CH3F conversion by quantum relaxation were clarified. It includes, first of all, the knowledge of the most important levels in CH3F which contribute substantially to the conversion through mixing by intramolecular perturbations. Second, the mixing mechanism in 13CH3F is shown to be the spin-spin interaction between the molecular nuclei. For 12CH3F, on the other hand, there is evidence that the spin-rotation perturbation is the most important while spin-spin interactions play a minor role. Third, the decay rate of the coherence between ortho and para states by collisions in the bulk was determined experimentally. All these data gave an internally consistent picture of the spin conversion in CH3F.

The mechanism responsible for nuclear spin conversion in CH3F was tested experimentally in a few ways. The most decisive experiments are the observation of level-crossing resonances in the conversion rate and the observation of the slowing down of the conversion with increasing gas pressure (“Quantum Zeno Effect”).

Prospects for further development in the field of spin isomers look optimistic. Even if one restrict oneself to the spin isomers separation method based on LID, there is a large variety of investigations possible. The LID effect already proved to be an efficient separation tool for a number of molecules like NH3, C2H4, H2O which all have nuclear spin isomers. There is no doubt that investigations of molecular spin isomers similar to that for CH3F can be performed with various other molecules.

## 7 ACKNOWLEDGMENTS

The results presented in this review were obtained in a long term project. We are indebted to many colleagues for fruitful and pleasant cooperation. More specifically, we would like to name the following colleagues (in the order in which they joined the project) V.N. Panfilov, V.P. Strunin, L.N. Krasnoperov, A.E. Bakarev, D. Papoušek, J Demaison, B. Nagels, M. Schuurman, D.A. Roozemond, N. Calas, P. Bakker, E. Ilisca, M. Irac-Astaud, K. Bahloul.

This project was made possible by financial support from the Netherlands Organization for Scientific Research (NWO), the Russian Academy of Sciences and the RFBR grant 98-03-33124a.

TABLE 1. Close ortho-para level pairs in CH3F and calculated conversion rates ($`\gamma `$) induced by spin-spin ($`SS`$) and spin rotation ($`SR`$) interactions.

|  | level pair | $`\omega _{\alpha ^{}\alpha }/2\pi ^{(1)}`$ | $`\gamma _{SS}/P`$ | $`\gamma _{SR}/P`$ |
| --- | --- | --- | --- | --- |
| Molecule | $`J^{},K^{}`$-$`J,K`$ | (MHz) | (10-3 s-1/torr) | (10-3 s-1/torr) |
| 13CH3F | 11,1-9,3 | 130.99$`\pm `$0.15 | 7.7 |  |
|  | 21,1-20,3 | -351.01$`\pm `$0.16 | 4.4 | 1.7(2) |
| 12CH3F | 9,2-10,0 | 8591.7$`\pm `$0.3 | 9.3$`10^3`$ | 1.3$`10^3`$ |
|  | 15,7-17,6 | 1745.7$`\pm `$2.3 | 6.8$`10^3`$ |  |
|  | 28,5-27,6 | 1189.2$`\pm `$1.5 | 16$`10^3`$ | $`0.3^{(3)}`$ |
|  | 51,4-50,6 | -41.3$`\pm `$2.5 | 28$`10^3`$ | 0.1 |

(1)Molecular parameters for 13CH3F from  and for 12CH3F from .

(2)Calculated assuming spin-rotational tensor component C22=1 kHz .

(3)Calculated assuming spin-rotational tensor component C21=3.6 kHz and a value for $`\mathrm{\Gamma }=210^7`$ s-1/torr .