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# Three-body recombination into deep bound states in a Bose gas with large scattering length

## Abstract

An effective field theory for the three-body system with large scattering length $`a`$ is applied to three-body recombination into deep bound states in a Bose gas. The recombination constant $`\alpha `$ is calculated to first order in the short-distance interactions that allow the recombination. For $`a<0`$, the dimensionless combination $`m\alpha /(\mathrm{}a^4)`$ is a periodic function of $`\mathrm{ln}|a|`$ that exhibits resonances at values of $`a`$ that differ by multiplicative factors of 22.7. This dramatic behavior should be observable near a Feshbach resonance when $`a`$ becomes large and negative.

One important factor limiting the achievable density in Bose-Einstein condensates (BEC’s) of trapped atoms is the loss of atoms through 3-body recombination . Such losses occur when three atoms scatter to form a molecular bound state and a third atom. The kinetic energy of the final-state particles allows them to escape from the trapping potential. This process provides a unique window on 3-body dynamics of cold atoms. In a BEC, 3-body loss rates could also reveal new collective mechanisms involving a molecular condensate .

The recombination event rate can be parametrized as $`\nu _{rec}=\alpha n^3`$, where $`\alpha `$ is the recombination constant and $`n`$ the density of the gas. The calculation of $`\alpha `$ in general is a complicated problem, because it is sensitive to the detailed behavior of the interaction potential. If the $`s`$-wave scattering length $`a`$ is large compared to the size of the atoms, however, the problem simplifies. Assuming that $`a`$ is the only important length scale, dimensional analysis implies $`\alpha =𝒞\mathrm{}a^4/m`$, where $`m`$ is the mass of the atoms and $`𝒞`$ is dimensionless. For $`a>0`$, there can be 3-body recombination into a shallow $`s`$-wave state with binding energy $`\mathrm{}^2/(ma^2)`$. For either sign of $`a`$, there can also be recombination into deep molecular bound states. The coefficient $`\alpha `$ can then be split into two contributions $`\alpha _S`$ and $`\alpha _D`$ coming from recombination into the shallow and deep bound states, respectively.

The 3-body recombination into the shallow bound state has been studied in Refs. . For the $`s`$-wave contribution, $`𝒞`$ is an oscillatory function of $`\mathrm{ln}a`$:

$$\alpha _S67.9\mathrm{cos}^2[s_0\mathrm{ln}(a\mathrm{\Lambda }_{})+1.74]\frac{\mathrm{}a^4}{m}(a>0),$$
(1)
where $`s_01.0064`$ and $`\mathrm{\Lambda }_{}`$ is the 3-body parameter introduced in Ref. . In the adiabatic hyperspherical approximation, the oscillatory behavior can be explained by interference between paths connecting two hyperspherical potentials . Within the framework of effective field theory, this unique behavior is due to scaling violations created by a 3-body interaction required for consistent renormalization . For $`a<0`$, there is no shallow bound state (there is a low-energy virtual state instead) and $`\alpha _S0`$.

Effective field theory (EFT) is a powerful method for describing systems composed of particles with wave number $`k`$ much smaller than the inverse of the characteristic range $`R`$ of their interaction. EFT focuses on the universal long-distance aspects of the problem, by modelling the interactions as pointlike . For wave numbers $`k1/R`$, one can expand in powers of the small variable $`kR`$. Generically, the scattering length $`a`$ is comparable to $`R`$, and the expansion is effectively in powers of $`ka`$. In the case of large scattering length $`aR`$, the dependence on $`ka`$ must be treated nonperturbatively. In the EFT, a single 3-body parameter is necessary and sufficient to renormalize the ultraviolet divergences at leading order in $`kR`$ . The scattering length and this 3-body parameter describe all low-energy 3-body observables up to errors of order $`R/a`$.

In this Letter, we use EFT methods to study the recombination constant $`\alpha _D`$ for deep bound states. The deep bound states are outside the range of the effective theory and cannot be treated explicitly. Nevertheless, their contribution to 3-body recombination can be calculated within the EFT by using the optical theorem (cf. Fig. 1(a)).

The 3-body recombination channels generate imaginary parts in the $`33`$ scattering amplitude. The imaginary part from recombination into the shallow bound state is dynamically generated in the EFT. The imaginary part from 3-body recombination into deep bound states can be taken into account by adding a local interaction term to the EFT.

A similar approach has been used successfully to describe the effects of the annihilation decays of positronium in QED and heavy quarkonium in QCD within the framework of nonrelativistic EFT’s . The annihilation of positronium into photons involves intermediate states with relativistic electrons and positrons that are outside the range of validity of the EFT. However, the effects of the annihilation process on $`e^+e^{}`$-scattering at low energies can be taken into account systematically by adding local 4-fermion operators with imaginary coefficients to the effective Lagrangian. In the case of recombination into a molecule with binding energy $`B\mathrm{}^2/(ma^2)`$, the molecule and the recoiling atom will emerge with large momenta of order $`\sqrt{mB}`$ which is outside the domain of the EFT. Up to corrections of order $`p^2/(mB)`$, where $`p`$ is the scale of the momentum of the three atoms, the effect of the recombination process on the $`33`$ scattering amplitude can be taken into account with a local 3-body interaction term whose coefficient has an imaginary part. The interaction is local, because the three atoms have to approach to within a distance of order $`\mathrm{}/\sqrt{mB}a`$ to recombine. The imaginary 3-body coefficient accounts collectively for recombination into all deep bound states. It could in principle be calculated if the 2- and 3-body potentials describing the interactions between atoms were known with sufficient accuracy. In practice, it has to be determined from experimental data. Once this parameter is fixed, the dependence of $`\alpha _D`$ on $`a`$ and $`\mathrm{\Lambda }_{}`$ can be predicted.

In Ref. , we have calculated $`\alpha _S`$ for a large, positive scattering length $`a`$. In the following, we extend this work to calculate $`\alpha _D`$ for large $`a`$ of either sign. For simplicity, we now set $`\mathrm{}=1`$. We start with a local Lagrangian for a nonrelativistic boson field $`\psi `$ and an auxiliary field $`d`$ with the quantum numbers of two bosons :

$``$ $`=`$ $`\psi ^{}\left(i{\displaystyle \frac{}{t}}+{\displaystyle \frac{\stackrel{}{}^2}{2m}}\right)\psi +d^{}d`$ (2)
$``$ $`{\displaystyle \frac{g}{\sqrt{2}}}(d^{}\psi \psi +\psi ^{}\psi ^{}d)+(h+ih^{})d^{}d\psi ^{}\psi +\mathrm{},`$ (3)
where $`h^{}`$ is the free parameter accounting for recombination into the deep states. The dots denote terms with more derivatives and/or fields; those with more fields do not contribute to the 3-body amplitude, while those with more derivatives are suppressed at low energy. The couplings $`g`$ and $`h`$ in Eq. (2) can be eliminated in favor of $`a`$ and $`\mathrm{\Lambda }_{}`$, respectively. The atom propagator has the usual nonrelativistic form $`i/(\omega p^2/2m)`$. The 2-atom scattering amplitude for incoming atoms with momenta $`\pm \stackrel{}{k}`$ has the form $`(1/aik)^1`$. The exact propagator for $`d`$ has a pole at $`\omega =1/(ma^2)+\stackrel{}{p}^{\mathrm{\hspace{0.17em}2}}/(4m)`$ corresponding to the shallow bound state .

Before describing the calculation of $`\alpha _D`$, we summarize the calculation of $`\alpha _S`$ in Ref. . The coefficient for recombination into the shallow bound state can be expressed as $`\alpha _S=512\pi ^2\left|t(p_f)\right|^2/(\sqrt{3}m)`$, where $`t(p)`$ is the amplitude for the transition between three atoms at rest and a final state consisting of an atom and a shallow $`s`$-wave state with momentum $`p`$ in their center-of-momentum frame. This amplitude is evaluated on shell at the value $`p_f=2/(\sqrt{3}a)`$ prescribed by energy conservation. However, $`t(p)`$ is also defined at off-shell values of $`p`$ as the solution of an integral equation that contains the 2- and 3-body interaction terms . Note that $`t`$ is related to the amplitude $`T`$ of Ref.  via $`t(p)=mT(p)/(48\pi ^{3/2}\sqrt{a})`$. The integral equation is regularized by a momentum cutoff $`\mathrm{\Lambda }`$. All observables can be made independent of the cutoff by adjusting the 3-body coefficient $`h(\mathrm{\Lambda })`$ as a function of $`\mathrm{\Lambda }`$. The evolution of $`h`$ with $`\mathrm{\Lambda }`$ approaches a limit cycle: $`\mathrm{\Lambda }^2h`$ varies periodically between $`+\mathrm{}`$ and $`\mathrm{}`$ as $`\mathrm{\Lambda }`$ increases by multiplicative factors of $`\mathrm{exp}(\pi /s_0)22.7`$ . Since all observables are cutoff independent, we can choose a $`\mathrm{\Lambda }`$ for which $`h(\mathrm{\Lambda })=0`$. The 3-body parameter $`\mathrm{\Lambda }_{}`$ then appears in the upper limit of the integral and we obtain a renormalized equation ,

$`t(p)={\displaystyle \frac{2}{p^2}}+{\displaystyle \frac{2}{\pi }}{\displaystyle _0^{\mathrm{\Lambda }_n}}{\displaystyle \frac{dqq^2t(q)}{1/a+\sqrt{3}q/2iϵ}}`$ (4)
$`\times {\displaystyle \frac{1}{pq}}\mathrm{ln}\left|{\displaystyle \frac{q^2+pq+p^2}{q^2qp+p^2}}\right|,`$ (5)
with $`\mathrm{\Lambda }_n=\mathrm{\Lambda }_{}\mathrm{exp}[(n\pi +\mathrm{arctan}(1/s_0))/s_0]`$ and $`s_01.0064`$. The integer $`n`$ should be large enough that errors of $`𝒪(1/(\mathrm{\Lambda }_na))`$ can be neglected. In practice, one can often choose $`n=1`$. Solving the integral equation for $`t(p)`$ and evaluating the solution as described above, we obtain the result in Eq. (1). The integral equation (4) also has a solution for $`a<0`$, but there is no shallow bound state in this case and $`\alpha _S=0`$.

In order to describe the recombination into the deep bound states, we use the optical theorem as discussed above and include an imaginary part $`h^{}`$ in the coefficient of the 3-body contact interaction. We assume that the $`h^{}`$ term can be treated as a perturbation at first order. However, the external legs have to be dressed with initial and final state interactions to all orders. We have to calculate the diagrams shown in Fig. 1(b), where the blob represents the solution of Eq. (4) and the triangle represents an insertion of $`ih^{}`$. This leads to

$`\alpha _D={\displaystyle \frac{288\pi ^2a^2}{m}}{\displaystyle \frac{h_1}{\mathrm{\Lambda }_n^2}}\left|1+{\displaystyle \frac{2}{\pi }}{\displaystyle _0^{\mathrm{\Lambda }_n}}{\displaystyle \frac{dqq^2t(q)}{1/a+\sqrt{3}q/2iϵ}}\right|^2,`$ (6)
where we have defined $`h^{}/(mg^2)=h_1/\mathrm{\Lambda }_n^2`$. Eq. (6) gives a renormalized expression for $`\alpha _D`$ up to corrections of $`𝒪(1/(\mathrm{\Lambda }_na))`$. Since $`t(q)`$ is known numerically from solving Eq. (4), the calculation of $`\alpha _D`$ entails the numerical evaluation of the integral in Eq. (6).

There are now two cases to consider: $`a>0`$ and $`a<0`$. We first consider the case $`a>0`$. Evaluating Eq. (6), we find that the amplitude is dominated by a linear divergence in the integral and is proportional to $`\mathrm{\Lambda }_na`$. The factors of $`\mathrm{\Lambda }_n`$ cancel and the result is proportional to $`a^4`$ with a coefficient that, within the numerical accuracy, is independent of $`\mathrm{\Lambda }_{}a`$:

$$\alpha _D=0.041h_1\frac{\mathrm{}a^4}{m}(a>0).$$
(7)
In Fig. 2(a), we show both $`\alpha _S`$ and $`\alpha _D`$ for $`a>0`$, with $`h_1`$ adjusted such that $`\alpha _D=10`$. The recombination into the deep bound states fills in the zeroes of $`\alpha _S`$, so that they become at best local minima of the recombination rate.

We now turn to the more interesting case $`a<0`$. Evaluating Eq. (6), we find that the amplitude is again dominated by a linear divergence in the integral. However, the coefficient of $`a^4/m`$ is not a pure number but exhibits scaling violations. $`\alpha _D`$ has the remarkable dependence on $`\mathrm{\Lambda }_{}|a|`$ shown in Fig. 2(b). The coefficient diverges at a sequence of values of $`\mathrm{\Lambda }_{}|a|`$ that are equally spaced on a logarithmic scale. To a high numerical accuracy, the results can be described by the formula

$$\alpha _D=\frac{5.61h_1}{\mathrm{sin}^2[s_0\mathrm{ln}(\mathrm{\Lambda }_{}|a|)+1.77]}\frac{\mathrm{}a^4}{m}(a<0).$$
(8)
The oscillatory dependence on $`\mathrm{ln}|a|`$ is in accord with a general scaling law by Efimov . There are divergences whenever $`s_0\mathrm{ln}(\mathrm{\Lambda }_{}|a|)+1.77`$ is an integer multiple of $`\pi `$. They occur because a 3-body Efimov state  has been tuned to threshold by the variation of $`a`$. The divergences are artifacts of the first order perturbation theory in $`h_1`$, which treats the Efimov states below the 3-body threshold as having sharp energies. However, these Efimov states aquire a width that depends on $`h_1`$ from recombination into the deep states . This will change the divergences into resonances at which the recombination rate is enhanced by a factor $`(\mathrm{}^2/\mathrm{\Gamma }ma^2)^2`$, where $`\mathrm{\Gamma }`$ is the width of an Efimov state at the 3-body threshold. First-order perturbation theory in $`h_1`$ is justified if $`\mathrm{\Gamma }\mathrm{}^2/(ma^2)`$, except within $`\mathrm{\Gamma }`$ of a resonance. The determination of the height of the resonance peaks requires a calculation that is nonperturbative in $`h_1`$. Note that the elastic 3-body scattering amplitude will also exhibit these resonances if $`a<0`$. For $`a>0`$, an Efimov state at the 3-body threshold has a width of order $`\mathrm{}^2/(ma^2)`$ from recombination into the shallow 2-body bound state. Consequently, there should be no resonances in the recombination rate.

The EFT results for $`\alpha `$ depend on two parameters $`\mathrm{\Lambda }_{}`$ and $`h_1`$ that are determined by interatomic interactions at distances much smaller than $`|a|`$. They have predictive power only if $`a`$ can be varied as a function of some external parameter and if the dependence of $`\mathrm{\Lambda }_{}`$ and $`h_1`$ on that parameter is known. One case in which there is predictive power is near a Feshbach resonance, where $`a`$ is varied by tuning a molecular bound state close to the threshold of two atoms by using an external magnetic field $`B`$. Short-distance parameters must be smooth functions of $`B`$. Over the narrow interval of a Feshbach resonance, they can be approximated by a linear or even constant function of $`B`$. Linear dependence of the short-distance parameter $`g`$ in (2) corresponds to $`a(B)=a_0+\mathrm{\Delta }/(BB_0)`$, where $`a_0`$ is the off-resonant scattering length and $`\mathrm{\Delta }`$ is the width of the Feshbach resonance. The short distance parameters $`\mathrm{\Lambda }_{}`$ and $`h_1`$ can be approximated by constants near the resonance at $`B_0`$.

In Fig. 3 we compare our theory with measurements of the atom loss rate coefficient $`K_3=3\alpha `$ in an ultracold gas of 85Rb-atoms by Roberts et al. . In 85Rb, there is a Feshbach resonance with width $`\mathrm{\Delta }=11.5`$ G at a magnetic field $`B_0=155.2`$ G . In Fig. 3, the scattering length is negative below the Feshbach resonance at $`B_0=155.2`$ G and positive above. Consequently, the shallow bound state contributes to $`K_3`$ only above the resonance. The free parameter $`h_1=24.7`$ has been fixed to reproduce the overall magnitude of $`K_3`$ below the resonance. For $`a>0`$, this value of $`h_1`$ leads to a contribution of the deep bound states to the loss rate ($`K_{3D}`$) that is much smaller than the contribution of the shallow bound state ($`K_{3S}`$) except near the minima of $`K_{3S}`$. One might be able to determine $`h_1`$ experimentally from the depth of these minima. In Fig. 3, we have plotted $`K_{3D}`$ and $`K_{3S}`$ for two values of the 3-body parameter: $`\mathrm{\Lambda }_{}=5/\text{a.u.}`$ and $`\mathrm{\Lambda }_{}=20/\text{a.u.}`$. The parameter $`\mathrm{\Lambda }_{}`$ would be determined very accurately if a local minimum or maximum in the loss rate were observed.

Divergences in the 3-body recombination rate for $`a<0`$ have been observed previously by Esry et al. . They calculated $`\alpha `$ numerically for various 2-body potentials, most of them with a single bound state (either shallow or deep). They varied $`a`$ from large negative values to large positive values by tuning the depth of the potential. For $`a>0`$, $`\alpha /a^4`$ increases to a maximum at some value $`a_{\mathrm{max}}`$ and then decreases to an interference minimum as predicted by Eq. (1). For $`a<0`$, $`\alpha /a^4`$ diverges at some value $`a_{\mathrm{div}}`$. The ratio $`|a_{\mathrm{div}}|/a_{\mathrm{max}}`$ ranged from 1.6 to 2 for the potentials studied. Since the maxima of $`\alpha _S/a^4`$ and the divergences of $`\alpha _D/a^4`$ in Fig. 2 appear at the same values of $`|a|`$, the EFT predicts $`|a_{\mathrm{div}}|/a_{\mathrm{max}}=1`$. The discrepancy between the results of Ref.  and the EFT prediction can be explained by a variation in the effective short-distance parameters $`\mathrm{\Lambda }_{}`$ and $`h_1`$ as the depth of the potential is tuned to vary $`a`$. Near a Feshbach resonance, the short distance behavior of the potential is essentially unchanged as $`B`$ is varied. Thus $`\mathrm{\Lambda }_{}`$ and $`h_1`$ should be nearly constant and the EFT prediction should hold as long as $`|a|`$ is much larger than its off-resonance value.

We have shown that the EFT approach to the 3-body system with large scattering length can be applied to recombination into deep bound states. For $`a>0`$, this contribution fills in the interference minima of the recombination rate into shallow bound states, transforming them into local minima of the total recombination rate. For $`a<0`$, the EFT approach makes the dramatic prediction that the recombination rate for zero-momentum atoms should exhibit resonances due to Efimov states at a sequence of values for $`a`$ that differ by multiplicative factors of $`\mathrm{exp}(\pi /s_0)22.7`$. Provided the widths of these Efimov states are numerically small compared to $`\mathrm{}^2/(ma^2)`$, the resonances should be observable as sharp peaks in the recombination rate near a Feshbach resonance.

We thank C.H. Greene and J.P. Burke for useful discussions and for providing us with numerical results of their calculations. This research was supported by NSF grant PHY-9800964 and DOE grant DE-FG02-91-ER4069.


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# 1 In the usual case, the fermionic spectrum contains two lines (solid) that describe zero modes boosted in the 𝑧-direction. One line describes the left-moving and the other the right-moving zero modes. Perturbations of the bosonic background can mix the two zero modes at the origin and convert them into two massive modes that lie on hyperbolae. The points on the two hyperbolae are related by CP transformations as shown.

Neutrino Zero Modes and Stability of Electroweak Strings

Dejan Stojkovic

Department of Physics
Case Western Reserve University
Cleveland, OH 44106-7079, USA

## Abstract

We discuss massless and massive neutrino zero modes in the background of an electroweak string. We argue that the eventual absence of the neutrino zero mode implies the existence of topologically stable strings where the required non-trivial topology has been induced by the fermionic sector.

Recent experimental evidence strongly suggests that neutrinos are very light, but not massless. A simple way to extend the standard model such that it incorporates light neutrino masses is to add a singlet right-handed neutrino. The origin of $`M_R`$ is a vacuum expectation value of some scalar field, acquired at some energy scale much greater than that of the electroweak scale. $`M_R`$ can therefore be taken to be spatially homogeneous. The Lagrangian is:

$`_{SM}`$ $`=`$ $`{\displaystyle \frac{1}{4}}W_{\mu \nu }^aW^{a\mu \nu }{\displaystyle \frac{1}{4}}F_{\mu \nu }F^{\mu \nu }+\left(D_\mu \mathrm{\Phi }\right)^{}\left(D^\mu \mathrm{\Phi }\right)\lambda \left(\mathrm{\Phi }^{}\mathrm{\Phi }\eta ^2\right)^2`$
$``$ $`i\overline{\mathrm{\Psi }}\gamma ^\mu D_\mu \mathrm{\Psi }i\overline{e_R}\gamma ^\mu D_\mu e_R+h^{}\left(\overline{e_R}\mathrm{\Phi }^{}\mathrm{\Psi }+\overline{\mathrm{\Psi }}\mathrm{\Phi }e_R\right)`$
$`+`$ $`h\left[\overline{\mathrm{\Psi }}i\tau _2\mathrm{\Phi }^{}\nu _R+\overline{\nu _R}\mathrm{\Phi }^T(i\tau _2)^{}\mathrm{\Psi }\right]+{\displaystyle \frac{1}{2}}\overline{\nu _R^c}M_R^{}\nu _R+{\displaystyle \frac{1}{2}}\overline{\nu _R}M_R\nu _R^c`$
with $`\mathrm{\Psi }(\nu _L,e_L^{})^T`$, $`\mathrm{\Phi }(\varphi ^+,\varphi )^T`$, $`\nu _L^T=(\alpha ,\beta ,\alpha ,\beta )`$, $`\nu _R^T=(\gamma ,\delta ,\gamma ,\delta )`$, $`\nu ^cC\overline{\nu }^T`$ and with the usual definition of the gauge and Higgs fields and covariant derivatives . In the Z-string ansatz, all the gauge and Higgs fields are zero except:

$$Z^\mu (0,\frac{v(r)}{r}\stackrel{}{e}_\theta ),\varphi =\eta f(r)e^{i\theta }$$
(2)
where $`v(r)`$ and $`f(r)`$ are the Z-string profile functions. The neutrino equations of motion are:

$`i\gamma ^\mu D_\mu \nu _L`$ $`=`$ $`h\varphi ^{}\nu _R`$
$`i\gamma ^\mu _\mu \nu _R`$ $`=`$ $`h\varphi \nu _L+M_R(\nu _R)^c`$ (3)
Using the ansatz for $`\beta `$, $`\beta =_{m=\mathrm{}}^{\mathrm{}}i\beta _m(r)e^{ik_zzi\omega t+im\theta }`$ and similarly for the other spinor components , after setting $`\omega =k_z=0`$, we get a set of recursive equations for the coefficients $`\beta `$ and $`\gamma `$:

$`\beta _m^{}+{\displaystyle \frac{(m+v)}{r}}\beta _m`$ $`=`$ $`h\eta f\gamma _m`$
$`\gamma _m^{}{\displaystyle \frac{m}{r}}\gamma _miM_R\gamma _{1m}^{}`$ $`=`$ $`h\eta f\beta _m`$ (4)
An analytic solution to the system (S0.Ex4) could not be found, but we can learn something about the structure of solutions by looking at their asymptotic behavior. For $`m=0`$, at large r, where $`f1`$, $`v1`$ the system (S0.Ex4) has four solutions for each spinor component. Two of them are exponentially growing while two are exponentially decaying. Only the latter ones are physically acceptable. For small $`r`$ where, $`vv_0r^2`$ and $`ff_0r`$, the structure of the system (S0.Ex4) is such that only three solutions are well behaved i.e. nonsingular and singe valued. With three well-behaved solutions at the origin and two well-behaved solutions at infinity there must be at least one solution which is well-behaved everywhere. Each of the two well-behaved solutions at infinity matches on to a unique linear combination of all four solutions at the origin where only one of them is bad, so there is always one linear combination of the two good solutions at infinity which does not have any contribution from the single bad solution at the origin. We conclude that in this case there is always one well behaved zero mode solution.

In the case of massless neutrino, for large $`r`$, $`\omega 0`$ and $`m=0`$, we get Bessel’s equation for $`\beta `$,

$$\beta _0^{\prime \prime }+\frac{1}{r}\beta _0^{}+\beta _0(\omega ^2\frac{1}{r^2})=0$$
(5)
with the general solution given by a linear combination of Bessel’s functions:

$$\beta _0(\omega r)=A\sqrt{\omega }J_1(\omega r)+B\sqrt{\omega }Y_1(\omega r)$$
(6)
where $`A`$ and $`B`$ are constants. We see, therefore, that the solution is properly $`\delta `$-function normalized. In the zero mode limit $`\omega 0`$. Using the asymptotic expansion for Bessel’s function of small argument we get $`\beta _01/r`$ which is the result found in most of the literature. The usual interpretation is that this state is not normalizable. If we look at the solution for $`\beta _0`$ as an isolated zero mode, it is obviously not normalizable because the normalization integral diverges logarithmically for large $`r`$. But, we have seen that this state is actually part of a continuum spectrum of the theory and is Dirac delta function normalizable. Therefore it is a valid zero mode solution. (A similar analysis can be done for zero modes of massive and massless fermions in the background of a domain wall .)

In the most general case , the presence of a constant left-handed Majorana mass, $`M_L`$, could destroy the neutrino zero mode. The left-handed Majorana mass terms have the form:

$$\overline{\nu _L}M_L\nu _L^c+\overline{\nu _L^c}M_L^{}\nu _L.$$
(7)
It was shown in  that for a certain range of mass parameters the neutrino zero mode does not exist on a electroweak string. We will argue that this fact imply the existence of the phenomenon which we call “topology induced by fermions”.

The possibility of not having a neutrino zero mode while the corresponding electron zero mode is still present is important from the point of view of the string stability under perturbations. In the usual case with a pair of zero modes (see Fig. (1)), perturbations in the Higgs and gauge sectors mix the two zero modes and convert them into two low lying massive states. If the neutrino zero mode is not present, perturbations of the string cannot lift the electron zero mode into a massive mode without violating CP invariance (see Fig. (2)) (the bosonic background is CP invariant since we can absorb all the CP violating phases into the spinor components). This conclusion that a single zero mode can not be removed from the spectrum, obtained from pure symmetry consideration, can be confirmed by studying the stability of fermionic zero modes on electroweak strings under perturbations . For non-topological strings this conclusion seems paradoxical because there is no topology in the bosonic sector that prevents the string from decaying into the vacuum. However, there is no electron zero mode in the vacuum. The only resolution seems to be that the absence of the neutrino zero mode provides topological stability to the string and that the topology enters via the fermionic sector of the model.

It is difficult to incorporate a constant $`M_L`$ into the standard model as a vacuum state. The source of $`M_L`$ could be the vacuum expectation value of an $`SU(2)_L`$ Higgs triplet $`\mathrm{\Delta }`$. The coupling of $`\mathrm{\Delta }`$ to the lepton doublet is given by $`\overline{\mathrm{\Psi }^c}i\tau _2\mathrm{\Delta }\mathrm{\Psi }`$ . The kinetic terms in the Lagrangian now contain the covariant gradient of the Higgs triplet which couples $`\mathrm{\Delta }`$ to the Z-gauge field. This coupling forces a solution of the bosonic equations of motion for $`\mathrm{\Delta }`$ to wind around the Z-string and hence to vanish on the string axis. Similarly, a cubic interaction term $`\mathrm{\Phi }^{}i\tau _2\mathrm{\Delta }\mathrm{\Phi }^{}`$ forces the triplet to wind due to $`\theta `$ dependence of $`\mathrm{\Phi }`$ . The way to avoid the problem of coupling to the gauge fields is to set all the standard model gauge fields to zero. In this case the gauge groups become global. We can also set a cubic interaction term $`\mathrm{\Phi }^{}i\tau _2\mathrm{\Delta }\mathrm{\Phi }^{}`$ to zero. This can be done by requiring the lepton number conservation in the initial Lagrangian. If we consider the situation in which the doublet and the triplet get vacuum expectation values:

$$\mathrm{\Phi }=\left(\begin{array}{c}0\\ \eta f(r)e^{i\theta }\end{array}\right),\mathrm{\Delta }=\left(\begin{array}{cc}0& 0\\ M_L& 0\end{array}\right)$$
(8)
the symmetry breaking pattern is $`SU(2)_L\times U(1)_YU(1)_Q`$ where all the symmetry groups are global. The model, although not the standard model anymore, supports a spatially homogeneous $`M_L`$ and the non-topological global Z-string, and the above discussion applies to it.

From the other point of view, if we want to keep all the features of the standard model, at a given moment of time, one can consider fermions with the general mass matrix in the background of the standard model Z-string. We again consider the symmetry breaking pattern (8). As is characteristic for a phase transition phenomenon, the Higgs and gauge fields, initially take different random configurations at different regions in space. One of the possible configurations we would like to analyze is a configuration in which $`\varphi `$ winds around some axis while $`M_L`$ and $`M_R`$ are constant. If a non-trivial topology was present in the bosonic sector of the model, such a configuration would be stable. However the present model does not have any non-trivial bosonic topology. A configuration with the constant $`M_L`$ is not a solution of the equations of motion and does not minimize the energy. Usually, such a non-equilibrium configuration evolves continuously into a state of minimum energy which, in this case, is the vacuum where all the fields are constant, unless there are topological sectors which forbid the evolution from one sector to another. The bosonic sector of the standard model does not contain such topological sectors. However, if the parameters of the model are such that there is no neutrino zero mode , then the constant $`M_L`$ configuration supports a single electron zero mode. As we have argued, CP invariance forbids removing (or creating) a single zero mode and different configurations can not continuously transform into one another.

Although we did not show that there is a topological charge density which can be associated with this “fermionic topology”, we showed that there is an integer $`n_Ln_R`$ (the difference between the left- and right- moving fermionic zero modes, namely electron and neutrino zero modes) that characterizes the field configuration. We argue that $`n_Ln_R`$ plays the role of the topological charge and cannot change under continuous evolution of the fields. Since $`n_Ln_R`$ in the vacuum is zero while in our chosen background is 1, the background and the vacuum are in distinct topological sectors. Thus, the configuration with a single electron zero mode leads to a stable string where the non-trivial topology arises from the fermionic sector of the theory and not, as is usual, from the non-trivial topology associated with the bosonic vacuum manifold.

A real challenge would be a construction of an index theorem describing this phenomenon. In this case, there should exist a topological charge density associated with this “fermionic topology”. Unlike the all known versions of (topological) index theorems which take only the bosonic field configurations into account, this new index theorem must also depend on the fermionic sector of the theory.


text:
# Acoustic Plasmons in MgB₂

\[

## Abstract

We present strong evidence for the existence of an acoustic plasmon mode, that is, a quadrupolar charge collective mode with linear dispersion, in $`\mathrm{MgB}_2`$. This mode may be responsible for the anomalously small value of the Coulomb pseudopotential required to explain the high superconducting transition temperature of $`40\mathrm{K}`$.

\]

The recent discovery of superconductivity in $`\mathrm{MgB}_2`$  has spurred a wave of activity both on the experimental and on the theoretical side. The transition temperature of $`T_c=39.5\mathrm{K}`$ is by far the highest found in any binary compound. With the exception of $`\mathrm{C}_{60}`$, it is surpassed only by the high-temperature copper-oxide superconductors. A detailed analysis of the electron-phonon interaction finds relatively strong coupling to a high frequency phonon mode . However, the observed $`T_c=39.5\mathrm{K}`$ could be obtained only by assuming that the Coulomb pseudopotential takes an anomalously small value, $`\mu ^{}0.02`$ — a value roughly seven times smaller than for usual $`s`$-$`p`$ superconductors. Here, we propose that an acoustic plasmon mode exists in $`\mathrm{MgB}_2`$. This leads to an attractive contribution, thereby lowering the value of the Coulomb pseudopotential.

The idea of acoustic plasmons goes back to Pines , and, following Fröhlich, has been considered as a mechanism for superconductivity in the transition metals in the past . In the presence of two carrier species with very different effective masses, the light carriers can act to screen the Coulomb repulsion between the heavy carriers, and thereby lower the plasma frequency of the heavy carriers. The resulting plasmon mode will have a linear dispersion $`\omega _a=v_aq`$ (hence the term acoustic plasmon), where $`v_a`$ is of the order of (but somewhat higher than) the Fermi velocity of the heavy carriers. The acoustic plasmon mode is Landau damped by decay into the electron-hole continuum of the light carriers, but for small wave vectors $`q`$ the mode will be located within the lower range of the electron-hole continuum, so that the damping may be weak, and the acoustic plasmon may exist as a well-defined collective mode.

Since no experimental evidence of acoustic plasmons could be found, and one was able to explain superconductivity in the transition metals within the usual phonon mechanism, interest in the topic began to wane in the late 1980’s. We believe that $`\mathrm{MgB}_2`$ is a good candidate for further research on acoustic plasmons and their contribution to superconductivity, due to its Fermi surface characteristics. These have been first reported in Ref. , and will be briefly described below:

$`\mathrm{MgB}_2`$ consists of honeycomb layers of boron atoms that are stacked vertically with no displacement. The magnesium atoms are located at the center of the hexagons formed by boron, but between the boron planes. The resulting structure is called the $`\mathrm{AlB}_2`$ structure. The in-plane lattice constant is $`a=3.086\mathrm{\AA }`$, while the interlayer spacing is $`c=3.524\mathrm{\AA }`$. Hence there is a strong anisotropy in the boron-boron bond lengths. To a good approximation, the outer shells of the $`\mathrm{Mg}`$ atoms can be assumed as being fully ionized, so that the boron system bears a certain resemblance with graphite, both structurally and electronically. The differences in the electronic properties of $`\mathrm{MgB}_2`$ and graphite are mainly due to the attractive potential of the $`\mathrm{Mg}`$ ions, which enhances the dispersion of the $`p_z`$-orbitals parallel to the $`c`$-axis through hybridization with the $`\mathrm{Mg}`$ $`s`$-orbital.

Carriers are situated in two hole bands derived from the $`\sigma `$-bonding boron $`p_{x,y}`$-orbitals, that are essentially two-dimensional, and in one electron and one hole band derived from the $`\pi `$-bonding boron $`p_z`$-orbitals (see Fig. 1). The smaller overlap of the latter in the $`x,y`$-directions compensates for the larger interatomic spacing in the $`z`$-direction, so that the $`\pi `$-bands are nearly isotropic.

An essential feature of the band structure is the large difference in the $`z`$-components of the Fermi velocities between the $`\sigma `$ hole bands and the $`\pi `$ electron and hole bands. As will be shown explicitly below, the existence of two different velocity scales gives rise to a weakly damped acoustic plasmon mode that corresponds to long-wavelength charge density fluctuations between these bands. While the total charge density $`\rho _\pi +\rho _\sigma `$ does not fluctuate, the charge difference $`\rho _\pi \rho _\sigma `$ will vary locally. Since the $`\sigma `$-orbitals are mainly located within the Boron planes, while the charge in the $`\pi `$-orbitals is situated between the planes, this charge transfer between the orbitals gives rise to quadrupolar charge fluctuations.

We will now show the existence of a well-defined acoustic plasmon mode within the random phase approximation (RPA). For our purpose it is convenient to define the polarization insertion $`\mathrm{\Pi }_{ab}`$ for different carrier species $`a`$ and $`b`$ as indicated in Fig. 2. For a single carrier species, $`\mathrm{\Pi }_{aa}`$ then reduces to the standard definition . The polarization insertion is related to the time-ordered density-density correlation function $`C_{ab}`$ between different types of carriers as

$$C_{ab}(𝐫,t)=i\mathrm{T}\stackrel{~}{n}_a(𝐫,t)\stackrel{~}{n}_b(0,0)=\mathrm{}\mathrm{\Pi }_{ab}(𝐫,t).$$
(1)
Here $`q=(𝐪,\omega )`$ is a momentum four-vector, $`U_0(q)=4\pi e^2/q^2`$ is the bare Coulomb potential, and $`\stackrel{~}{n}_a=n_an_a`$ denotes the fluctuations in the charge density of carrier species $`a`$. Specializing to the case of two carrier species of opposite charge (electrons and holes), we can express $`\mathrm{\Pi }_{ab}`$ in the random phase approximation as

$$\mathrm{\Pi }_{ab}^{\mathrm{rpa}}(q)=\frac{\delta _{ab}\mathrm{\Pi }_a^0(q)U_0(q)\mathrm{\Pi }_1^0(q)\mathrm{\Pi }_2^0(q)}{1U_0(q)\mathrm{\Pi }_1^0(q)U_0(q)\mathrm{\Pi }_2^0(q)},$$
(2)
where the lowest-order polarization insertion $`\mathrm{\Pi }_a^0`$ is given in terms of the non-interacting Green’s functions $`G_a^0`$ as

$$\mathrm{\Pi }_a^0(q)=\frac{2}{i\mathrm{}}\frac{d^4k}{(2\pi )^4}G_a^0(k)G_a^0(k+q).$$
(3)
We now define the total charge fluctuations $`n_{}=\stackrel{~}{n}_1\stackrel{~}{n}_2`$ and the charge transfer fluctuations $`n_+=\stackrel{~}{n}_1+\stackrel{~}{n}_2`$. Then the corresponding correlation functions are given by

$$\frac{1}{\mathrm{}}C_{}(q)=\frac{\mathrm{\Pi }_1^0(q)+\mathrm{\Pi }_2^0(q)}{1U_0(q)\mathrm{\Pi }_1^0(q)U_0(q)\mathrm{\Pi }_2^0(q)},$$
(4)
and

$$\frac{1}{\mathrm{}}C_+(q)=\frac{\mathrm{\Pi }_1^0(q)+\mathrm{\Pi }_2^0(q)4U_0(q)\mathrm{\Pi }_1^0(q)\mathrm{\Pi }_2^0(q)}{1U_0(q)\mathrm{\Pi }_1^0(q)U_0(q)\mathrm{\Pi }_2^0(q)}.$$
(5)
A collective mode corresponds to a pole in the correlation function in the complex frequency plane, and can thus be identified by the condition

$$\underset{a}{}\mathrm{\Pi }_a^0(q)=\frac{1}{U_0(q)},$$
(6)
which remains valid for more than two carrier species as well. For small wave vectors $`U_0(q)`$ will be very large, so that we can set the left-hand side to zero instead. Inserting the above condition into the numerator of Eq. (4), we see that the pole’s residue is proportional to $`1/U_0(q)q^2`$, so that fluctuations in the total charge density are suppressed for small wavevectors. Due to the additional term in the numerator of Eq. (5) this is not the case for the charge transfer fluctuations described by $`C_+`$.

We calculated the band structure with the tight-binding linear muffin-tin orbital (TBLMTO) method , and used the following analytical fits for our calculations of $`\mathrm{\Pi }^0`$: For the $`\sigma `$ bands,

$$ϵ(𝐤)=ϵ_0^{(\sigma )}+2t_z^{(\sigma )}\mathrm{cos}(k_zc)\frac{\mathrm{}^2}{2m_{1,2}}(k_x^2+k_y^2),$$
(7)
where $`ϵ_0^{(\sigma )}=0.66\mathrm{eV}`$, $`t_z^{(\sigma )}=0.22\mathrm{eV}`$, $`m_1=0.27m_e`$, and $`m_2=0.50m_e`$, with $`m_e`$ being the bare electron mass. For the $`\pi `$ bands we used

$`ϵ(𝐤)=ϵ_0^{(\pi )}2t_z^{(\pi )}\mathrm{cos}(k_zc)`$ (8)
$`\pm 2t_x\sqrt{{\displaystyle \frac{3}{4}}+{\displaystyle \frac{1}{2}}\mathrm{cos}(k_xa)+\mathrm{cos}({\displaystyle \frac{1}{2}}k_xa)\mathrm{cos}({\displaystyle \frac{\sqrt{3}}{2}}k_ya)},`$ (9)
where $`ϵ_0^{(\pi )}=0.16\mathrm{eV}`$, $`t_z^{(\pi )}=1.12\mathrm{eV}`$, $`t_x=1.73\mathrm{eV}`$, and the positive or negative sign corresponds to the electron and hole band, respectively.

Within the approximate dispersion given by Eq. (7), the lowest-order polarization insertion of the $`\sigma `$ bands can be calculated exactly for the special case where $`𝐪`$ is parallel to the $`z`$-axis:

$$\mathrm{\Pi }_{\sigma 1,2}^0(q\widehat{z},\omega )=\frac{m_{1,2}}{\pi \mathrm{}^2c}\left\{\frac{\theta (1Y^2)i\theta (Y^21)}{\sqrt{\left|1Y^2\right|}}1\right\},$$
(10)
where $`Y=4t_z^{(\sigma )}\mathrm{sin}(qc/2)/\mathrm{}\omega `$, and $`\theta (x)`$ is the Heaviside step function. For $`𝐪`$ off the z-axis and for the $`\pi `$-bands we resort to numerical calculations. Results are shown in Fig. 3. From the condition (6) we can identify an acoustic plasmon mode with dispersion $`\omega _a=v_aq`$, where the plasmon velocity is $`v_a1.78\mathrm{\AA }\mathrm{eV}=2.70\times 10^7\mathrm{cm}/\mathrm{s}`$. The acoustic plasmon mode is weakly damped by decay into the $`\pi `$ electron-hole continuum. The remaining two zeroes of $`\mathrm{Re}\mathrm{\Pi }^0`$ lie deep within the electron-hole continuum and correspond to overdamped modes, as can be seen from the large imaginary part of $`\mathrm{\Pi }^0`$. To estimate the damping coefficient $`\lambda `$ of the weakly damped mode we assume that the contribution from the $`\pi `$ carriers to the real and imaginary parts of $`\mathrm{\Pi }^0`$ is constant in the vicinity of $`\omega _a`$. Then the imaginary part of the pole’s location in the complex plane can easily be calculated from the analytic expression (10), and yields a Q-factor $`Q=\omega _a/\lambda 15`$. The acoustic plasmon mode is hence well-defined.

The above analysis leads us to propose that a well defined acoustic plasmon mode exists for small values of the transverse component $`q_{}`$. Physically this mode corresponds to quadrupolar charge fluctuations involving a local charge transfer between $`\sigma `$\- and $`\pi `$-orbitals of the boron atoms. This collective mode in turn leads to an attractive retarded contribution to the Coulomb interaction in a window in $`(𝐪,\omega )`$-space, which will modify the repulsive Coulomb pseudopotential. Further analysis is required to determine if the modification is strong enough to give the proposed reduction to a value of $`\mu ^{}=0.02`$.


text:
# Frustrated 3-Dimensional Quantum Spin Liquid in CuHpCl

## I Introduction

Organometallic magnets are excellent model systems in which to explore the intricate quantum many-body physics of interacting spin systems. They are attractive because their energy scales are well matched to efficient experimental probes of magnetism and because a wide range of magnetic phases are found in these materials. In addition to supporting frozen magnetic states with ferromagnetism, ferrimagnetism, antiferromagnetism and meta-magnetism, organometallic magnets also provide intriguing examples of quantum spin liquids. These can be defined as strongly correlated states of interacting spin systems where time reversal symmetry persists at temperatures far below the characteristic energy scale for interactions.

Quantum spin liquids are most commonly found in quasi-one-dimensional antiferromagnetic systems such as the uniform spin-1 chain, the alternating spin chain, and the spin-ladder. Low dimensionality generally enhances the phase space for low energy fluctuations,  and in one dimension, the effect is to preclude a frozen state involving Heisenberg spins.  However, there are also examples of spin-dimer systems where the singlet ground state associated with antiferromagnetically interacting spin pairs survives the effects of weaker inter-dimer interactions in two and three dimensions.

Geometrical frustration is an alternate route to strong fluctuations and there are theoretical predictions of quantum and classical spin liquids based on this effect. While materials that approximate kagomé and pyrochlore antiferromagnets generally have a freezing transition at sufficiently low temperatures, there are other more complex structures where geometrical frustration stabilizes an isolated singlet ground state in the $`T=0`$ limit. $`\mathrm{SrCu}_2(\mathrm{BO}_3)_2`$ is a three-dimensional version of the so-called Shastry-Sutherland model where the inter-dimer interactions are almost as strong as the intra-dimer interactions, and yet they fail to induce gapless magnetic fluctuations and long range order because no such state can satisfy all interactions. Frustration is also central to stabilizing the quasi-two-dimensional cooperative singlet state in the organometallic magnet PHCC. While in $`\mathrm{SrCu}_2(\mathrm{BO}_3)_2`$ correlations exist only within spin-dimers, the correlated spin clusters in PHCC involve at least 8 spins of which two spin pairs are frustrated and provide a positive contribution to the ground state energy. PHCC was previously identified as an alternating spin chain based on susceptibility measurements. This and other misidentifications indicate that conventional bulk measurements cannot reliably determine the origin and nature of spin systems with a gapped excitation spectrum and that more sophisticated techniques should be applied to explore these unique systems.

One magnet with a gapped excitation spectrum that has received considerable attention is $`\mathrm{Cu}_2(\mathrm{C}_5\mathrm{H}_{12}\mathrm{N}_2)_2\mathrm{Cl}_4`$ (Cu2(1,4-diazacycloheptane)2Cl4 , or for short CuHpCl).  Measurements of the magnetization, magnetic susceptibility, and specific heat show that this system has a spin gap $`\mathrm{\Delta }0.9`$ meV, a magnetic bandwidth of approximately 0.5 meV, and a saturation field $`H_{c2}=13.2`$ T. Based on these measurements and the crystal structure, it was proposed that CuHpCl is a two-leg spin ladder composed of coupled dimers, with the intra-dimer bonds of strength $`J_1=1.14`$ meV forming the rungs, and inter-dimer bonds of strength $`J_20.2J_1`$ forming the legs of the ladders.  Subsequent experimental results have generally been interpreted in terms of this model, and the system has been the inspiration for a number of theoretical studies.

Despite this extensive body of work, the true nature of the spin interactions in CuHpCl has never been conclusively demonstrated. Susceptibility and specific heat data are equally well described by spin-ladder, alternating chain, and coupled-bilayer models.  Some evidence that the two-leg ladder model might in fact not be appropriate for CuHpCl came from a previous inelastic neutron scattering experiment  on a powder sample, where we found that the wavevector-integrated magnetic scattering intensity did not show the characteristic van Hove singularities expected for the magnetic density of states of a one-dimensional spin system. In this measurement, the wavevector dependence of the energy-integrated magnetic scattering was also inconsistent with the predictions of the ladder model. However, conclusions from this experiment were limited by the coarse wavevector resolution of the instrument employed, and the large, non-magnetic background signal from the hydrogenous sample.

In this paper, we report inelastic neutron scattering measurements performed both on a deuterated powder with improved wavevector resolution and on hydrogenous single crystals. The powder and single-crystal measurements are each independently inconsistent with the spin-ladder model. The powder data indicate that the strongest dimer bond is different from that of the ladder model. The single crystal measurements show the presence of two modes within the 0.5 meV bandwidth, a feature not predicted by the spin-ladder model. Consideration of the measured dispersion relation and the structure of the system lead to the conclusion that the network of significant magnetic interactions in CuHpCl is three dimensional. Model-independent analysis of the powder and single-crystal data based on the first moment sum-rule provide the contributions of each crystallographically distinct spin pair to the ground state energy. Two classes of spin pairs yield positive contributions, indicating that geometrical frustration plays an important role in stabilizing the quantum spin liquid in CuHpCl.

### A Structure of CuHpCl

CuHpCl is monoclinic with space group $`P2_1/c`$ and room temperature lattice constants $`a=13.406(3)`$ Å, $`b=11.454(2)`$ Å, $`c=12.605(3)`$ Å, and $`\beta =115.01(2)^{}`$.  The low-temperature lattice constants measured with neutron scattering at $`T=4`$ K are $`a=13.35(4)`$ Å, $`b=11.24(6)`$ Å, $`c=12.72(4)`$ Å, and $`\beta =115.2(2)^{}`$. Figure 1 shows the approximately centro-symmetric binuclear molecular unit containing the spin pair denoted by bond 1 in Table 1. Each Cu2+ ion is in a (4+1) square pyramidal coordination with a Cl atom at the apex and the base formed by two N and two Cl atoms. Within the Cu($`\mu `$-Cl)2Cu complex of CuHpCl, the coordinating pyramids share apical edges and have parallel basal planes. Susceptibility measurements for a series of compounds with this atomic configuration indicate intra-molecular exchange constants ranging from -1.5 meV (ferromagnetic) to 0.9 meV (AFM) with no apparent correlation throughout the range of molecular structural parameters.

The intra-molecular exchange interactions in CuHpCl do not create an extended lattice. Because the molecular units in CuHpCl interact solely through hydrogen bonding, the dimensionality and the overall nature of magnetic interactions in this system are entirely determined by hydrogen bonding mediated exchange interactions. Owing to the slight deviation of the CuHpCl molecules from centro-symmetry, molecular pairs come in two flavors in the CuHpCl crystal structure, which we denote by a and b. Neglecting flavor distinctions, there are four configurations for molecular pairs in direct contact as shown in Fig. 2. The sublattices generated by each of these pairs are shown in Fig. 3. The numbers on Fig. 3 indicate possible spin exchange interactions mediated by hydrogen bonding and additional information about each of these is listed in Table 1. Each molecule is part of two molecular pairs of the type shown in Fig. 2(a). The three different exchange interactions associated with this molecular pair are denoted 2, 3, and 10 in Fig. 3 and Table 1. Bonds 2 and 3 proceed through a Cu-N-H-Cl-Cu path with H-Cl distances ranging from 2.3 Å to 2.7 Å. Bond 10 has a similar exchange pathway as for bonds 2 and 3 but must in addition traverse the entire Cu($`\mu `$-Cl)2Cu complex. The corresponding exchange interaction should therefore be significantly weaker than for bonds 2 and 3. Each molecule is also part of four pairs of the type shown in Fig. 2(b). Exchange pathways involving Cu-N-C-H-Cl-Cu mediate two different exchange interactions that we denote 4 and 7, with H-Cl bond distances ranging from 2.6 Å to 2.8 Å. Bond 7 should be negligible, however, as it involves an apical Cu-Cl contact. The same molecular pairs also afford an exchange interaction denoted by 8, which proceeds through a Cu-Cl-H-C-H-Cl-Cu pathway with H-Cl bond distances in the range 2.6-3.0 Å. Each molecule also is part of four molecular pairs of the type shown in Fig. 2(c). The exchange pathway involves either Cu-Cl-H-C-N-Cu or Cu-N-H-H-C-N-Cu with H-Cl and H-H bond lengths ranging from 2.7 Å to 3.1 Å. The corresponding exchange interactions are denoted 5 and 6. Finally, each molecule is also part of two molecular pairs of the type shown in Fig. 2(d) with displacement vectors $`\pm 𝐛`$. The exchange path passes through two 1,4 diazacycloheptane rings so the corresponding interactions are likely to be negligible, especially considering the lower coordination number for this interaction.

The molecular pairs in Fig. 2(a) and (d) yield one-dimensional lattices extending along the  and  directions respectively. Inter-molecular interactions corresponding to Figs. 2(b) and (c) on the other hand yield $`𝐛𝐜`$ and $`𝐚𝐛`$ spin planes with surface normals $`𝐚`$* and $`𝐜`$* respectively. Unfortunately it is difficult to predict the strength of hydrogen mediated exchange interactions, which reportedly can range from 0.1 meV to greater than 10 meV depending on the chemical environment. Previous papers on CuHpCl worked under the assumption that the inter-molecular bonds depicted in Fig. 2(a) are dominant, leading to the ladder model shown in Fig. 3(a). While we cannot provide firm quantitative information about the magnitude of inter-molecular exchange interactions, we shall present evidence that the 8 inter-molecular pairs of the type shown in Figs 2(b)-(c) when combined are energetically more significant than those shown in Fig. 2(a), and that the intra-molecular spin pair (1) is in a frustrated configuration.

## II Experimental Techniques

The powder sample studied consisted of 5.87 grams of deuterated CuHpCl. To produce this sample, perdeuterated 1,4-diazacycloheptane was first prepared following a previously published method.  The $`d_6`$-dibromopropane and $`N,N^{}`$-dibenzylethylene-$`d_4`$-diamine precursors required for this synthesis were prepared from commercially available 1,3-$`d_6`$-propanediol and ethylene-$`d_4`$-diamine, respectively. The CuHpCl powder was obtained by rapid cooling from $`40^{}`$C to $`0^{}`$C of 1:1 molar solutions of anhydrous $`\mathrm{CuCl}_2`$ and the deuterated 1,4-diazacycloheptane dissolved in the minimum amount of deuterated methanol. Prompt gamma neutron activation analysis performed on a portion of the sample confirmed $`95.0(1)\%`$ deuteration.

The single crystal measurements were performed on a composite sample with a total mass $`m110`$ mg. This sample consisted of four hydrogenous single crystals, mutually aligned to within 4.5 degrees. These crystals were obtained by diffusive growth from $`\mathrm{CuCl}_2`$ and 1,4-diazacycloheptane in methanol.  We have produced crystals as large as 33 mg using this method.

Inelastic neutron scattering measurements on both the powder and single-crystal samples were performed using the SPINS cold neutron triple axis spectrometer at the National Institute of Standards and Technology in Gaithersburg, Maryland. For the powder experiment, the horizontal beam collimation before the sample was $`50^{}/k_i`$-1) - 80. Scattered neutrons in the energy range $`2.6`$ meV $`E_f3.7`$ meV were Bragg reflected by a flat, 23 cm wide by 15 cm high pyrolytic graphite analyzer \[PG(002)\] at a distance of 91 cm from the sample position. The analyzer was followed by an $`80^{}`$ radial collimator and a position-sensitive detector. Cooled Be and BeO filters were employed before and after the sample, respectively. Data were collected by scanning the scattering angle $`2\theta `$ in the range $`7^{}`$ to $`114^{}`$ at fixed incident energy $`E_i`$. Scans at $`E_i=`$ 4.0, 4.34, and 4.84 probed inelastic scattering for energy transfer $`0.4`$ meV $`\mathrm{}\omega 2.09`$ meV and momentum transfer 0.2 Å-1 $`Q2.35`$ Å-1, with average full width at half maximum (FWHM) resolutions $`\delta \mathrm{}\omega =0.14`$ meV and $`\delta Q=0.014`$ Å-1. Backgrounds due to incoherent scattering from the analyzer and low-angle air scattering of the incident neutron beam were measured separately. After subtracting these, the data were converted to the normalized scattering intensity $`\stackrel{~}{I}(Q,\mathrm{}\omega )`$ using the measured incoherent elastic scattering from the sample following the procedure detailed in Ref. .

For the single-crystal measurements, the horizontal beam collimation before the sample was $`50^{}/k_i`$-1) - 80. A liquid nitrogen cooled BeO filter was placed after the sample and data were collected at fixed final energy $`E_f=3.7`$ meV while scanning the incident energy in the range $`3.95E_i5.45`$ meV. A horizontally-focusing pyrolytic graphite analyzer with horizontal and vertical acceptance angles of 5o and 7o respectively was used in conjunction with a single cylindrical detector, which subtended an angle of 4o in the horizontal plane to an area element of the analyzer. In this configuration the average instrumental energy resolution for the energy transfer range of 0.75 to 1.25 meV was $`\delta \mathrm{}\omega 0.17(1)`$ meV. Representative values of the projected FWHM wavevector resolution for the constant-Q scans performed throughout the measurement are $`\delta Q_{}=0.081`$ Å-1 and $`\delta Q_{}=0.065`$ Å-1 for the components of the wavevector transfer along the principal directions of the resolution ellipse at $`𝐐=(100)`$ and $`\mathrm{}\omega =1`$ meV. Scans at constant wavevector transfer were performed in both the ($`h0l`$) and ($`hk0`$) reciprocal lattice planes.

## III Results

### A Powder Sample Measurements

Figure 4 shows the normalized scattering intensity $`\stackrel{~}{I}(Q,\mathrm{}\omega )`$ for CuHpCl at $`T=0.3`$ K and $`T=30`$ K. At $`T=0.3`$ K, there is a band of inelastic scattering in the range of energy transfer $`0.9`$ meV $`<\mathrm{}\omega <`$ 1.4 meV, consistent with our previous measurements on a hydrogenous powder sample.  At $`T=30`$ K, the intensity in this Q-$`\mathrm{}\omega `$ range is diminished, which confirms that the corresponding inelastic scattering cross section is magnetic.

Figure 5 shows the wavevector averaged scattering intensity

$$\stackrel{~}{I}(\omega )=\frac{Q^2𝑑Q\stackrel{~}{I}(Q,\omega )}{Q^2𝑑Q}.$$
(1)
This data is a measure of the magnetic density of states. One-dimensional magnets have pronounced van Hove singularities at the upper and lower bounds of the magnetic excitation spectrum. When convolved with the energy resolution function, such singularities would produce the spectrum shown by the dashed line in Fig. 5. The inconsistency between model and data provides a first indication that CuHpCl is not a one dimensional spin system. A previous experiment led to the same conclusion and as it was done on a hydrogenous sample while the present sample is deutererated, the comparison of these experiments indicates that deuteration does not significantly alter magnetism in CuHpCl. Fig. 4(a) also shows that inelastic magnetic neutron scattering from CuHpCl is strongly peaked near $`Q_00.6`$ Å-1, with a secondary maximum near $`1.3`$ Å-1. The powder averaged scattering intensity from a single spin dimer with spacing $`d`$ has a peak for $`Q_0d=1.43\pi `$. The data thus indicate singlet formation in CuHpCl between spins separated by $`d1.43\pi /Q_0=7.5`$ Å. This result is also inconsistent with the ladder model for CuHpCl, as the dominant bond in this model is the intra molecular Cu pair (Fig. 1) whose spacing is only $`d_1=3.376`$ Å.

### B Single Crystal Measurements

Inelastic scattering measurements were carried out for wavevector transfers at the locations in the $`(h0l)`$ plane indicated on Fig. 6, as well as along the line $`(1k0)`$ perpendicular to this plane. Figures 7-11 show the data so obtained, while Figs. 12 and 13 summarize the corresponding dispersion relations derived by fitting the constant wavevector scans to resolution limited peaks.

When dynamic correlations are dominated by a single dimerized spin pair, there is a well tested RPA theory that can account for many aspects of the magnetic excitation spectrum.  As we shall show in the following, each spin in CuHpCl takes part in several strongly correlated spin pairs, so the RPA theory is not applicable in its present form. However, inspection of the excitation spectra and the crystal structure leads to important insights concerning the magnetism in CuHpCl.

We first note that there are two modes in the magnetic excitation spectrum. This is most easily seen at $`𝐐=(1,0.5,0)`$ in Fig. 7(c), where two resolution-limited peaks are clearly visible at $`\mathrm{}\omega =0.88`$ and 1.2 meV. Two modes are also visible at other wavevectors such as $`𝐐=(1.167,0,0)`$ in Fig. 8(b). In addition, Fig. 9(a) and Figs. 11(a-c) show broad or asymmetric peaks that are well described by a superposition of two resolution-limited Gaussian peaks.

The spin ladder and alternating chain models for CuHpCl corresponding to Fig. 3(a) and 3(d), respectively, both have a single degenerate triplet excitation and are therefore inconsistent with the observed two modes. This is true despite the fact that Cu($`\mu `$-Cl)2Cu complexes in CuHpCl come with two different orientations as the inter-molecular interactions in Fig. 2(a) and 2(d) only couple molecules with like orientations. However, the inter-molecular interactions in Fig. 2(b) and 2(c) link molecules with different orientations to form lattices with two molecules per unit cell \[Figs. 3(b) and 3(c)\]. If the ground and excited states maintain the full symmetry of the paramagnetic molecule and the spectrum is dominated by resonant modes, then any lattice except those in Figs. 3(a) and (d) has two triplet excited states consistent with the experimental data. This means that the lattices shown in Fig. 3(b) and/or 3(c) are essential parts of the interacting spin system in CuHpCl.

This conclusion is reinforced by Figs. 10 and 12(b), which show dispersion along the $`(h01h)`$ direction \[equivalent to $`(h0\overline{h})`$\]. With displacement vectors along  and , the molecular pairs in Fig. 2(a) and 2(d) cannot yield dispersion along this direction in reciprocal space. The implication is again that the inter-molecular interactions shown in Figs 2(b) and/or 2(c), and hence the lattices shown in Figs 3(b) and/or 3(c), are essential parts of the cooperative magnetic network in CuHpCl. Figures 8 and 12(c) show that there is also dispersion along the $`𝐚`$* direction. This implies that the interactions corresponding to Fig. 2(b) and 3(b) cannot be the only relevant inter-molecular interactions in the problem. Figures 11 and 13(a) show that there is dispersion along the $`𝐜`$* direction. Consequently the interactions corresponding to Fig. 2(c) and 3(c) also cannot be the only relevant inter-molecular interactions. By inference, at least two of the four types of inter-molecular interactions in Fig. 2 are important to cooperative magnetism in CuHpCl, and the interactions in Figs. 2(b) and/or 2(c) must be part of the group.

Figure 14 shows a projection of the lattice of interactions in CuHpCl along the $`𝐛`$ direction. The color-coding is consistent with Fig. 3 indicating bonds associated with different inter-molecular interactions. As the lattices of Fig. 3 interpenetrate, a corollary to the above is that CuHpCl is a three-dimensional interacting spin system. Nonetheless Figs. 7 and 13 show that there is less than 0.05 meV dispersion along $`𝐐=(1k0)`$. Based on the discussion above, the absence of dispersion along $`𝐛`$ cannot be due to lack of interactions that couple the system magnetically. A likely alternate explanation is that geometrical frustration localizes the excitations as has been observed in other geometrically frustrated systems.

## IV Analysis

### A Wavevector Dependent Intensity

The dynamic spin correlation function $`𝒮(𝐐,\omega )`$ obeys sum rules that can be used to draw additional model independent conclusions about magnetism in CuHpCl. The total moment sum rule provides an important check on whether the measured scattering intensity accounts for all spins in the sample:

$$\frac{d^3𝐐\mathrm{}𝑑\omega _\alpha 𝒮^{\alpha ,\alpha }(𝐐,\omega )}{d^3𝐐}=S(S+1).$$
(2)
The first moment sum rule provides a direct link between raw data and interaction terms in the spin Hamiltonian.

$`\mathrm{}\omega _𝐐`$ $``$ $`\mathrm{}^2{\displaystyle _{\mathrm{}}^{\mathrm{}}}\omega 𝒮^{\alpha \alpha }(𝐐,\omega )𝑑\omega `$ (3)
$`=`$ $`{\displaystyle \frac{1}{3}}{\displaystyle \frac{1}{N}}{\displaystyle \underset{𝐫,𝐝}{}}J_𝐝𝐒_𝐫𝐒_{𝐫+𝐝}(1\mathrm{cos}𝐐𝐝)`$ (4)
Here {d} is the set of all bond vectors connecting a spin to its neighbors, the index $`\{𝐫\}`$ runs over all $`N`$ spins. The Hamiltonian is assumed to take the form

$$=\frac{1}{2}\underset{𝐫,𝐝}{}J_𝐝𝐒_𝐫𝐒_{𝐫+𝐝},$$
(5)
For a powder sample, the magnetic component of $`\stackrel{~}{I}(Q,\mathrm{}\omega )`$ is related to the spherically averaged dynamic spin correlation function $`𝒮(Q,\omega )`$ by

$`\stackrel{~}{I}_m(Q,\mathrm{}\omega )`$ $`=`$ $`2{\displaystyle 𝑑Q^{}\mathrm{}𝑑\omega ^{}_{Q\omega }(QQ^{},\omega \omega ^{})}`$ (7)
$`|{\displaystyle \frac{g}{2}}f(Q^{})|^2𝒮(Q^{},\omega ^{}),`$
where $`_{Q\omega }(\delta Q,\delta \omega )`$ is the normalized instrumental resolution function,  $`f(Q)`$ is the magnetic form factor for Cu2+, and $`g`$ is the average $`g`$-factor, which is $`g=2.083`$ for CuHpCl.  Carrying out the integration of Eq. 2 for the band of intensity in Fig. 4(a) yields $`0.7(1)`$. The proximity of the value to $`S(S+1)=3/4`$ indicates that this band accounts for most of the magnetic scattering from CuHpCl. For a powder sample, the first moment $`\mathrm{}\stackrel{~}{\omega }_Q`$ of the measured quantity $`\stackrel{~}{I}_m(Q,\mathrm{}\omega )`$ is related to the spherical average of Eq. 4, and is given by

$`\mathrm{}\stackrel{~}{\omega }_Q`$ $``$ $`\mathrm{}^2{\displaystyle _{\mathrm{}}^{\mathrm{}}}\omega \stackrel{~}{I}_m(Q,\mathrm{}\omega )𝑑\omega `$ (8)
$`=`$ $`{\displaystyle \frac{2}{3}}|{\displaystyle \frac{g}{2}}f(Q)|^2{\displaystyle \frac{1}{N}}{\displaystyle \underset{𝐫,𝐝}{}}J_𝐝𝐒_𝐫𝐒_{𝐫+𝐝}\left(1{\displaystyle \frac{\mathrm{sin}Qd}{Qd}}\right),`$ (9)
where $`d=|𝐝|`$. The first moment $`\mathrm{}\stackrel{~}{\omega }_Q`$ computed from the data in Fig. 4(a) is shown in Fig. 15. In strongly dimerized systems, the term arising from the intra-dimer bond dominates the first moment. In the strongly dimerized two-leg ladder model of CuHpCl, these are the intra-molecular rung bonds labeled by 1 in Table 1 and depicted in Fig. 3(a). As shown by the dashed line in Fig. 15, the Q-dependence arising from inserting $`d_1`$ in Eq. 9 is manifestly inconsistent with the data. Specifically, the $`d_1=3.376`$ Å bond yields a maximum at higher Q than is observed in the experiment. Thus, a longer bond (or bonds) must give the dominant contribution to $`\mathrm{}\stackrel{~}{\omega }_Q`$. Fitting the data in Fig. 15 to Eq. 9 with a single, variable bond length $`d_\alpha `$ yields $`d_\alpha =7.5(2)`$ Å, and the dashed-dotted line shown in Fig. 15. However, this model is still inconsistent with the data. The salient discrepancy is that the ratio of the low-Q peak intensity to that of the high Q plateau is about twice larger in the data than in the model. Such a large ratio can only be achieved by combining terms of varying sign in Eq. 9. With appropriate spin spacings, $`d`$, such terms can interfere destructively in the high Q plateau while the low-Q regime is dominated by contributions from long bonds. Indeed, the solid line in Fig. 15, which we shall describe in greater detail below, corresponds to a model with both positive and negative terms in Eq. 9. According to this equation, the magnitude of the high-Q plateau is directly proportional to the shift of the ground state energy below zero while the peak height measures the strength of individual spin pair contributions to the ground state energy. Hence, there is a direct link between a large peak to plateau ratio in first moment data, and frustrated interactions that raise the ground state energy.

The single crystal data help to distinguish between the eight distinct spin pairs with Cu-Cu spacings in the range 7 to 7.6 Å. The first moment $`\mathrm{}\stackrel{~}{\omega }_𝐐`$ of the magnetic scattering intensity, $`\stackrel{~}{I}_m(𝐐,\mathrm{}\omega )`$, from a single crystalline sample is given by

$`\mathrm{}\stackrel{~}{\omega }_𝐐`$ $``$ $`\mathrm{}^2{\displaystyle _{\mathrm{}}^{\mathrm{}}}\omega \stackrel{~}{I}_m(𝐐,\mathrm{}\omega )𝑑\omega `$ (10)
$`=`$ $`{\displaystyle \frac{2}{3}}|{\displaystyle \frac{g}{2}}f(Q)|^2{\displaystyle \frac{1}{N}}{\displaystyle \underset{𝐫,𝐝}{}}J_𝐝𝐒_𝐫𝐒_{𝐫+𝐝}\left(1\mathrm{cos}𝐐𝐝\right).`$ (11)
Here we have neglected any spin space anisotropy, a reasonable assumption for a spin-1/2 quantum spin liquid. The first moment may be determined from gaussian fits to individual spectra as follows

$$\mathrm{}\stackrel{~}{\omega }_𝐐=\underset{i}{}\stackrel{~}{I}(𝐐)_i\mathrm{}\omega _i(𝐐),$$
(12)
where $`\stackrel{~}{I}_i(𝐐)`$ is the integrated intensity for mode $`i`$ at wavevector $`𝐐`$ and $`\mathrm{}\omega _i(𝐐)`$ is the corresponding mode energy. The wavevector dependence of $`\mathrm{}\stackrel{~}{\omega }_𝐐`$ is illustrated in Fig. 6 where the diameter of the circles is proportional to $`\mathrm{}\stackrel{~}{\omega }_𝐐`$ and as conventional plots along symmetry directions in Figs. 16 and 17. There is an undetermined overall scale factor as the single crystal data was not normalized in this experiment. The first moment is seen to be largest for $`h0.5`$ along the line $`(h01h)`$. Since the magnitude of Q in that part of reciprocal space is close to the value 0.55 Å-1 where the peak in the first moment of the powder data occurs, the powder and single crystal data are consistent. The strongest modulation in $`\mathrm{}\stackrel{~}{\omega }_𝐐`$ occurs along the $`(h0h)`$ direction, with weaker modulation also visible in other directions. From the form of Eq. 11, this implies that the bond vector that contributes most strongly to the first moment is parallel to .

To determine the relative importance of the magnetic bonds, we carried out a simultaneous fit of the powder data to Eq. 9 and the single-crystal data to Eq. 11 with a single set of values for the bond energies, $`J_𝐝𝐒_0𝐒_𝐝`$. Because their contributions to the first moment of the scattering data cannot be distinguished, we derive only an average correlation term for spin pairs labeled with the same numerical index in Table I. Such spin pairs would be equivalent had the molecular unit possessed centro-symmetry. In addition, there is close similarity between the chemical environments along the exchange pathway of a and b labeled bonds. These facts lend some support to the assumption that the corresponding bond energies are similar.

The results of the fit are given in the last column of Table I and as solid lines in Figs. 15\- 17. It is important to note the direct contribution of a spin pair to the ground state energy is small when the exchange constant and/or the spin correlation function is small. Furthermore, according to Eq. 5, negative bond energies lower the ground state energy while positive terms indicate a frustrated spin pair that raises the ground state energy.

## V Discussion

The most remarkable result from Table 1, is that the intra-molecular bond 1 is in a frustrated configuration. The presence of a frustrated spin pair with a short bond vector was anticipated based on inspection of the raw powder first moment data. It is easily verified that in a closed loop of interacting spins with an odd number of antiferromagnetic exchange interactions, only an even number of spin pairs can be satisfied. Bond 1 is part of no fewer than 5 near neighbor bond triangles that are frustrated if all interactions are antiferromagnetic. Figure 3(a) shows two of these triangles: (1,3,2) and (1,3,10). Fig. 3(b) shows bond triangles (1,4,8) and (1,4,7), while Fig. 3(c) shows bond triangle (1,5,6). Of these, Table 1 clearly indicates that the triangles in Fig. 3(b) are frustrated. Our analysis indicates that bonds 4 and 8 are satisfied at the apparent expense of bond 1. The energy derived for bond 7 while negative, is not statistically significant. This is consistent with the expectation from section I A that this is a weak exchange interaction.

The connectivity of the lattice formed by bonds 1, 4, and 8 is that of the geometrically frustrated Shastry-Sutherland model (SSM) albeit with lower symmetry. Compared to the SSM, which can be described as a square lattice with alternating diagonal bonds on half the squares, the lattice shown by solid lines in Fig. 3(b) corresponds to a tetragonal lattice formed by bonds 4 and 8 with the “diagonal” bonds 1 arranged as in the SSM. When the square lattice exchange interactions in the SSM are less than 70% of the interactions across the diagonal, the ground state of the SSM consists of singlets on every cross bond. For stronger inter-dimer interactions, there is a first order transition to square lattice Néel order. Table 1 indicates that the SSM planes in CuHpCl have local spin correlations resembling the Néel phase of the SSM. The lattice formed by bonds 1, 5, and 6 also has the topology of the SSM but correlations in this plane do not readily map on a known phase of the SSM.

It does seem surprising that spin pair 1 can provide a three times larger positive contribution to the ground state energy than the negative contributions from bonds 4 and 8. To determine whether this is plausible, we examined a series of frustrated antiferromagnetic spin-1/2 clusters. A central spin pair, $`𝐒_a,𝐒_b`$ with antiferromagnetic exchange constant $`J>0`$ is surrounded by $`2n`$ spins-1/2 $`𝐒_1,𝐒_2,\mathrm{}𝐒_{2n}`$, which interact with both pair members with equal antiferromagnetic exchange, $`J^{}>0`$. The spin Hamiltonian is given by

$``$ $`=`$ $`_0+_{2n}`$ (13)
$`_0`$ $`=`$ $`J𝐒_a𝐒_𝐛`$ (14)
$`_{2n}`$ $`=`$ $`J^{}{\displaystyle \underset{i=1}{\overset{2n}{}}}𝐒_i(𝐒_a+𝐒_b)`$ (15)
We examined clusters with $`n`$ ranging from 1 to 3. For each cluster we diagonalized the spin Hamiltonian and determined the ground state frustration index

$$f=4n\frac{<0|_0|0>}{<0|_{2n}|0>}$$
(16)
as a function of $`x=J^{}/J`$ in the range where the central spin pair is frustrated. We obtained maximum frustration indexes $`f_{max}=1,2,3`$ for $`n=1,2,3`$ respectively. The results show that a level of frustration similar to that observed for the intra-molecular spin pair in CuHpCl is possible even for very small spin clusters.

While the lattice of Fig. 3(b) provides an explanation for the frustration of bond 1, it does not readily account for the singlet ground state of CuHpCl. Local correlations in these planes is Néel-like so the lattice left on its own might be expected to have a gapless spectrum and long range order at low temperatures. From Table 1 we see that bond 3, which generates the lattice in Fig. 3(a), is in an un-frustrated configuration. In fact, this bond provides the greatest contribution towards lowering the ground state energy. Fig. 14 shows how the lattices of Figs. 3(a)-(c) intersect to form a three dimensional lattice. We see that if the lattice in Fig. 3(b) were in a Néel phase, then bond 3 only serves to strengthen such Néel order and extend it to three dimensions. It is therefore difficult to see how the sub-lattices from Figs. 3(a) and 3(b) alone can account for an isolated singlet ground state.

This leads us to the suggestion that bonds 5 and 6 could play a significant role even if the corresponding bond energies appear to be small. As is apparent from Fig. 14, bonds 5 and 6 close a molecular triangle that projects onto the $`𝐚𝐜`$ plane. The description therefore emerges of a set of antiferromagnetic SSM layers normal to $`𝐚^{}`$ coupled in a frustrating triangular lattice geometry to a second interpenetrating set of frustrated SSM layers normal to $`𝐛^{}`$. A small alternation between the 3a and 3b bonds that couple layers could be an additional factor favoring singlet formation on the stronger of these bonds.

The magnetic ground state energy may be calculated from Eq. 5 and the numbers in Table 1 to be -0.36 meV per spin. For comparison, if all bonds were satisfied with the same magnitude of spin correlations as observed the ground state energy would be -1.17 meV per spin. The ratio between the actual ground state energy and the latter upper bound on the energy in the absence of frustration is 0.3. For comparison the ground state energy of the SSM at the critical point separating the Néel phase and the dimer phase is 0.26 times the energy that the spin system would have if all bonds could simultaneously be engaged in singlet formation. Hence, CuHpCl is at least as frustrated as the SSM at its critical point.

## VI Conclusions

In summary, we have presented inelastic neutron scattering data from deuterated powder and hydrogenous single crystals of the organometallic spin-1/2 magnet CuHpCl. Consideration of the excitation spectra, the crystal structure, and the wave vector dependence of the first moment leads to the conclusion that spin-spin interactions in this system form a complex three-dimensional lattice and not a spin ladder as previously thought. While structurally one might expect CuHpCl to fall in the spin-dimer class of quantum spin liquids, this appears not to be the case. The spin gap in spin dimer systems is a consequence of the singlet ground state of individual dimers. However, in CuHpCl the intra molecular spin interaction is in a frustrated configuration so this cannot be the dominant interaction in the problem. Furthermore, if the intra-molecular interaction is antiferromagnetic, as expected, then the ground state features triplet molecules that in and of themselves cannot explain a gap in the excitation spectrum. We are therefore led to the conclusion that the pronounced gap in the excitation spectrum of CuHpCl is a consequence of the frustration inherent to this particular three-dimensional network of interactions. This is a surprising discovery as the symmetry of the lattice is low. On the other hand, the structure clearly is riddled with triangular units, and the connectivity between them is relatively low. These ingredients are known to be important for suppressing Néel order and promoting a spin liquid state. Further progress in understanding the magnetism of CuHpCl would benefit from accurate determination of H/D positions using neutron scattering, followed by quantum chemical calculations of exchange constants. More extensive measurements of the magnetic excitation spectrum are also needed, but these must await progress in crystal growth or neutron scattering instrumentation.

There are many organometallic quantum magnets that have been labeled as quasi-one-dimensional, based largely on the observation of a spin gap. Our experiments on CuHpCl have shown how neutron scattering from single crystals as small as 0.1 g can be used to establish the dimensionality and the basic nature of interacting spin systems. They also show that insulating magnets with a gap in their excitation spectrum may constitute a considerably more complex and diverse class of interacting quantum many body systems than previously anticipated.

## VII Acknowledgments

We thank R. Paul for help with neutron activation analysis. This work was supported by NSF Grants DMR-9801742 and DMR-0074571. DHR acknowledges the support of the David and Lucile Packard Foundation. TL acknowledges the support of the Sloan and Dreyfus Foundations. X-ray characterization was carried out using facilities maintained by the JHU MRSEC under NSF Grant number DMR-0080031. This work utilized neutron research facilities supported by NIST and the NSF under Agreement No. DMR-9986442.


text:
# Transmission of a Cartesian Frame by a Quantum System

## Abstract

A single quantum system, such as a hydrogen atom, can transmit a Cartesian coordinate frame (three axes). For this it has to be prepared in a superposition of states belonging to different irreducible representations of the rotation group. The algorithm for decoding such a state is presented, and the fidelity of transmission is evaluated.

There has recently been considerable progress in devising ways to indicate a spatial direction by means of quantum particles. This type of information cannot be represented by a sequence of symbols like 0 and 1, unless the emitter (Alice) and the receiver (Bob) have prearranged a common coordinate system for specifying the numerical values of relevant angles. Physical objects have to be sent. Preceding works \[1–4\] have considered the use of spins for transmitting a single direction. The simplest method  is to send these spins polarized along the direction that one wishes to indicate. This, however, is not the most efficient procedure: when two spins are transmitted, a higher accuracy is achieved by preparing them with opposite polarizations . If there are more than two spins, optimal results are obtained with entangled states .

This Letter presents a method for the transmission of a complete Cartesian frame. If many spins are available, a simple possibility would be for Alice to use half of them for indicating her $`x`$ axis and the other half for her $`y`$ axis. However, the two directions found by Bob may not then be exactly perpendicular, because of quantum “uncertainties.” Some adjustment will be needed to obtain the best estimates for the $`x`$ and $`y`$ axes before Bob can infer from them his guess of Alice’s $`z`$ direction. This method is not optimal, and it is obviously not possible to proceed in this way if a single quantum messenger is available. Here we shall show how a single hydrogen atom (formally, a spinless particle in a Coulomb potential) can transmit a complete frame.

Consider the $`n`$-th energy level of that atom (a Rydberg state). Its degeneracy is $`d=n^2`$ because the total angular momentum may take values $`j=0,\mathrm{},n1`$, and for each one of them $`m=j,\mathrm{},j`$. Alice indicates her $`xyz`$ axes by sending the atom in a state

$$|A=\underset{j=0}{\overset{n1}{}}\underset{m=j}{\overset{j}{}}a_{jm}|j,m,$$
(1)
with normalized coefficients $`a_{jm}`$ that will be specified below. Bob then performs a covariant measurement  in order to evaluate the Euler angles $`\psi \theta \varphi `$ that would rotate his own $`xyz`$ axes into a position parallel to Alice’s axes. Bob’s detectors (ideally, there is an infinite number of them ) have labels $`\psi \theta \varphi `$ and the mathematical representation of his apparatus is a positive operator valued measure (POVM) , namely a resolution of identity by a set of positive operators:

$$d_{\psi \theta \varphi }E(\psi \theta \varphi )=\mathrm{𝟏},$$
(2)
where $`d_{\psi \theta \varphi }\mathrm{sin}\theta d\psi d\theta d\varphi /8\pi ^2`$ is the $`SO(3)`$ Haar measure for Euler angles , and $`E(\psi \theta \varphi )=|\psi \theta \varphi \psi \theta \varphi |`$. The vectors $`|\psi \theta \varphi `$ will be specified below. The probability that the detector labelled $`\psi \theta \varphi `$ is excited is given by

$$P(\psi \theta \varphi )=A|d_{\psi \theta \varphi }E(\psi \theta \varphi )|A=d_{\psi \theta \varphi }|A|\psi \theta \varphi |^2.$$
(3)
Our task is to construct vectors $`|\psi \theta \varphi `$ such that Eq. (2) is satisfied (that is, the probabilities sum up to one) and Bob’s expected error is minimal.

Following the method of Ref. , we define a fiducial vector for Bob,

$$|B=\underset{j=0}{\overset{n1}{}}\sqrt{2j+1}\underset{m=j}{\overset{j}{}}b_{jm}|j,m,$$
(4)
where the coefficients $`b_{jm}`$ are normalized for each $`j`$ separately:

$$\underset{m=j}{\overset{j}{}}|b_{jm}|^2=1j.$$
(5)
In Ref.  a single value of $`m`$ was used; here we need all the values. Note that Eq. (1) was written with Alice’s notations ($`m`$ is the angular momentum along her $`z`$ axis), while Eq. (4) is written with Bob’s notations ($`m`$ refers to his $`z`$ axis). This issue will be dealt with later.

We now define

$$|\psi \theta \varphi =U(\psi \theta \varphi )|B,$$
(6)
where $`U(\psi \theta \varphi )`$ is the unitary operator for a rotation by Euler angles $`\psi \theta \varphi `$. Note that since $`|B`$ is a direct sum of vectors, one for each value of $`j`$, then likewise $`U(\psi \theta \varphi )`$ is a direct sum with one term for each irreducible representation,

$$U(\psi \theta \varphi )=\underset{j}{}𝒟^{(j)}(\psi \theta \varphi ),$$
(7)
where the $`𝒟^{(j)}(\psi \theta \varphi )`$ are the usual irreducible unitary rotation matrices . To prove that Eq. (2) is satified, we note that its left hand side is invariant if multiplied by $`U(\mu \nu \rho )`$ on the left and $`U(\mu \nu \rho )^{}`$ on the right, for any arbitrary Euler angles $`\mu \nu \rho `$ (because these unitary matrices represent group elements and therefore have the group multiplication properties) . It then follows from a generalization of Schur’s lemma  that the left hand side of (2) is a direct sum of unit matrices, owing to the presence of the factor $`(2j+1)`$ which is the dimensionality of the corresponding irreducible representation. Therefore Eq. (2) is satisfied.

The detection probability (3) can thus be written as $`P(\psi \theta \varphi )=d_{\psi \theta \varphi }|A|U(\psi \theta \varphi )|B|^2.`$ To compute this expression explicitly, we must use a uniform system of notations for $`|A`$ and $`|B`$ — recall that Eq. (1) was written in Alice’s basis, and Eq. (4) in Bob’s basis. It is easier to rewrite Alice’s vector $`|A`$ in Bob’s language. For this we have to introduce the Euler angles $`\xi \eta \zeta `$ that rotate Bob’s $`xyz`$ axes into Alice’s axes (that is, $`\xi \eta \zeta `$ are the true, but unknown values of the angles $`\psi \theta \varphi `$ sought by Bob). The unitary matrix $`U(\xi \eta \zeta )`$ represents an active transformation of Bob’s vectors into Alice’s. Therefore, $`U(\xi \eta \zeta )^{}`$ is the passive transformation \[7, p. 216\] from Bob’s notations to those of Alice, and $`U(\xi \eta \zeta )`$ is the corresponding transformation from Alice’s notations to Bob’s. Written in Bob’s notations, Alice’s vector $`|A`$ becomes $`U(\xi \eta \zeta )|A`$ so that, in Eq. (3), $`A|`$ becomes $`A|U(\xi \eta \zeta )^{}`$. Let us therefore define

$$U(\alpha \beta \gamma )=U(\xi \eta \zeta )^{}U(\psi \theta \varphi ).$$
(8)
The Euler angles $`\alpha \beta \gamma `$ have the effect of rotating Bob’s Cartesian frame into his estimate of Alice’s frame, and then rotating back the result by the true rotation from Alice’s to Bob’s frame. That is, the angles $`\alpha \beta \gamma `$ indicate Bob’s measurement error, and the probability of that error is

$$P(\alpha \beta \gamma )=d_{\alpha \beta \gamma }|A|U(\alpha \beta \gamma )|B|^2,$$
(9)
where $`d_{\alpha \beta \gamma }=\mathrm{sin}\beta d\alpha d\beta d\gamma /8\pi ^2`$. Note that in the above equation $`|A`$ is written with Alice’s notations as in (1), and $`|B`$ with Bob’s notations as in (4).

Of course Bob cannot know the values of $`\alpha \beta \gamma `$. His measurement only yields some value for $`\psi \theta \varphi `$. The following calculation that employs $`\alpha \beta \gamma `$ has the sole purpose of estimating the expected accuracy of the transmission (which does not depend on the result $`\psi \theta \varphi `$).

We must now choose a suitable quantitative criterion for that accuracy. When a single direction is considered, it is convenient to define the error  as $`\mathrm{sin}(\omega /2)`$, where $`\omega `$ is the angle between the true direction and the one estimated by Bob. The mean square error is

$$\mathrm{sin}^2(\omega /2)=(1+\mathrm{cos}\omega )/2=1F,$$
(10)
where $`F`$ is usually called the fidelity . When we consider a Cartesian frame, we likewise define fidelities for each axis. Note that $`\mathrm{cos}\omega _k`$ (for the $`k`$-th axis) is given by the corresponding diagonal element of the orthogonal (classical) rotation matrix. Explicitly, we have

$$\mathrm{cos}\omega _z=\mathrm{cos}\beta ,$$
(11)
and

$$\mathrm{cos}\omega _x+\mathrm{cos}\omega _y=(1+\mathrm{cos}\beta )\mathrm{cos}(\alpha +\gamma ),$$
(12)
whence, by Euler’s theorem,

$$\mathrm{cos}\omega _x+\mathrm{cos}\omega _y+\mathrm{cos}\omega _z=1+2\mathrm{cos}\mathrm{\Omega },$$
(13)
where $`\mathrm{\Omega }`$ has a simple physical meaning: it is the angle for carrying one frame into the other by a single rotation.

The expectation values of these expressions are obtained from Eq. (9):

$$f(\alpha \beta \gamma )=d_{\alpha \beta \gamma }|A|U(\alpha \beta \gamma )|B|^2f(\alpha \beta \gamma ),$$
(14)
where, explicitly,

$$A|U(\alpha \beta \gamma )|B=\underset{j,m,r}{}a_{jm}^{}b_{jr}j,m|𝒟^{(j)}(\alpha \beta \gamma )|j,r.$$
(15)
The unitary irreducible rotation matrices $`𝒟^{(j)}(\alpha \beta \gamma )`$ have components

$$j,m|𝒟^{(j)}(\alpha \beta \gamma )|j,r=e^{i(m\alpha +r\gamma )}d_{mr}^{(j)}(\beta ),$$
(16)
where the $`d_{mr}^{(j)}(\beta )`$ can be expressed in terms of Jacobi polynomials. Collecting all these terms, we finally obtain, after many tedious analytical integrations over products of Jacobi polynomials ,

$$f(\alpha \beta \gamma )=f_{jkmnrs}a_{jm}^{}b_{jr}a_{kn}b_{ks}^{},$$
(17)
where the numerical coefficients $`f_{jkmnrs}`$ depend on our choice of $`f(\alpha \beta \gamma )`$. The problem is to optimize the components $`a_{jm}`$ (normalized to 1), and $`b_{jm}`$ satisfying the constaints (5), so as to maximize the above expression. For further use, it is convenient to define a matrix

$$M_{jm,kn}=\underset{r,s}{}f_{jkmnrs}b_{jr}b_{ks}^{},$$
(18)
so that

$$f(\alpha \beta \gamma )=M_{jm,kn}a_{jm}^{}a_{kn}=A|M|A.$$
(19)
First consider a simple case: to transfer only the $`z`$ axis, we wish to maximize $`\mathrm{cos}\beta `$. An explicit calculation yields

$$f_{jkmnrs}=\delta _{mn}\delta _{rs}g_{jk}.$$
(20)
The matrix $`g_{jk}`$ which is defined by the above equation has nonvanishing elements

$$g_{jj}=ns/[j(j+1)],$$
(21)
and

$$g_{j,j1}=g_{j1,j}=\frac{1}{j}\sqrt{\frac{(j^2n^2)(j^2s^2)}{4j^21}}.$$
(22)
The $`\delta _{mn}`$ term in (20) implies that, for any choice of Bob’s fiducial vector $`|B`$, the matrix $`M`$ in (19) is block-diagonal, with one block for each value of $`m`$. The optimization of Alice’s signal results from the highest eigenvalue of that matrix. This is the highest eigenvalue of one of the blocks, so that a single value of $`m`$ is actually needed. A similar (slightly more complicated) argument applies if Alice’s vector is given and we optimize Bob’s fiducial vector. This result proves the correctness of the intuitive assumption that was made in  where a single value of $`m`$ was used. It was then found that when $`m=0`$ (the optimal value) the expected error asymptotically behaves as $`1.446/d`$, where $`d`$ is the effective number of Hilbert space dimensions. In the present case, $`d=(j_{\mathrm{max}}+1)^2`$, which is the degeneracy of the $`n`$-th energy level.

If we want to transfer two axes, we use Eq. (12) and calculate the matrix elements for $`(1+\mathrm{cos}\beta )\mathrm{cos}(\alpha +\gamma )`$. (It is curious that they are simpler than those for $`\mathrm{cos}(\alpha +\gamma )`$ alone.) We obtain

$$f_{jkmnrs}=\delta _{m,n1}\delta _{r,s1}h_{jk}+\delta _{n,m1}\delta _{s,r1}h_{kj},$$
(23)
where the nonvanishing elements of $`h_{jk}`$ are

$`h_{jj}`$ $`=`$ $`{\displaystyle \frac{[(jn+1)(j+n)(js+1)(j+s)]^{1/2}}{2j(j+1)}},`$ (24)
$`h_{j,j1}`$ $`=`$ $`{\displaystyle \frac{[(jn+1)(jn)(js+1)(js)]^{1/2}}{2j(4j^21)^{1/2}}},`$ (25)
$`h_{j1,j}`$ $`=`$ $`{\displaystyle \frac{[(j+n1)(j+n)(j+s1)(j+s)]^{1/2}}{2j(4j^21)^{1/2}}}.`$ (26)
Note that the $`h_{jk}`$ matrix, whose elements depend on $`n`$ and $`s`$, is not symmetric (while $`g_{jk}`$ was). This is because it comes from the operator $`e^{i(\alpha +\gamma )}`$ which is not Hermitian. However the two terms of (23) together, which corresponds to $`\mathrm{cos}(\alpha +\gamma )`$, have all the symmetries required by the other terms $`a_{jm}^{}b_{jr}a_{kn}b_{ks}^{}`$ in Eq. (17). Finally, if we wish to optimize directly the three Cartesian axes (without losing accuracy by inferring $`z`$ from the approximate knowledge of $`x`$ and $`y`$) we use all the terms of (13), that is, both those of (20) and of (23).

It now remains to find the vectors $`|A`$ and $`|B`$ that minimize the transmission error. For small values of $`j`$, we used Powell’s method  without imposing any restrictions on $`|A`$ and $`|B`$ other than their normalization conditions. As intuitively expected, we found that the optimal vectors satisfy

$$b_{jm}=a_{jm}\left(\underset{n}{}|a_{jn}|^2\right)^{1/2},j.$$
(27)
This means that Bob’s vector should look as much as possible as Alice’s signal, subject to the restrictions imposed by the constraint (5).

Taking this property for granted is the key to a more efficient optimization method, as follows: assume any $`b_{jm}`$, so that the bilinear form (18) is known. Find its highest eigenvalue and the corresponding eigenvector $`a_{jm}`$. From the latter, get new components $`b_{jm}`$ by means of (27), and repeat the process until it converges (actually, a few iterations are enough). The results are shown in Fig. 1. It is seen that there is little advantage in optimizing only two axes, if for any reason the third axis is deemed less important. If the three axes are simultaneously optimized, the mean square error (per axis) asymptotically tends to $`3.168d^{0.586}`$.

It is not surprising that this result is weaker than the one for a single axis, which was $`1.446/d`$. The obvious reason is that we are now transmitting a three-dimensional rotation operation that can be applied to any number of directions, not only to three orthogonal axes. Indeed, consider any set of unit vectors $`𝐞_m^\mu `$, where $`m=1,2,3`$, and $`\mu `$ is a label for identifying the vectors. Let $`w_\mu `$ be a positive weight factor attached to each vector, indicating its importance. Let $`R(\alpha \beta \gamma )`$ be the classical orthogonal rotation matrix  for Euler angles $`\alpha \beta \gamma `$. Then the cosine of the angle between Bob’s estimate of $`𝐞_m^\mu `$ and the true direction of that vector is

$$\mathrm{cos}\omega _\mu =\underset{m,n}{}R_{mn}(\alpha \beta \gamma )𝐞_m^\mu 𝐞_n^\mu .$$
(28)
With the same notations as before, we have

$$f(\alpha \beta \gamma )=\underset{\mu }{}w_\mu \mathrm{cos}\omega _\mu =\underset{m,n}{}R_{mn}(\alpha \beta \gamma )C_{mn},$$
(29)
where

$$C_{mn}=\underset{\mu }{}w_\mu 𝐞_m^\mu 𝐞_n^\mu .$$
(30)
This is a positive matrix which depends only on the geometry of the set of vectors whose transmission is requested. We can now diagonalize $`C_{mn}`$ and write it in terms of three orthogonal vectors, possibly with different weights. Therefore, no essentially new features follow from considering more than three directions.

Finally, we note that all the above calculations, as well as those in preceding works \[1–4\], assume that Alice and Bob have coordinate frames with the same chirality (this can be checked locally by using weak interactions). If the chiralities are opposite, then all the directions inferred by Bob should be reversed (because directions are polar vectors while spins are axial vectors).

In summary, we have shown that a single structureless quantum system (a point mass in a Coulomb potential) can transfer information on the orientation of a Cartesian coordinate system with arbitrary accuracy. No classical carrier would be able to achieve this result, unless it has an asymmetric internal structure. This is one more example of the remarkable ability of quantum systems to encode information more efficiently than classical ones.

We thank Ramon Muñoz-Tapia for helpful comments. Work by AP was supported by the Gerard Swope Fund and the Fund for Encouragement of Research. PFS was supported by a grant from the Technion Graduate School.

FIG. 1. Mean square error (per axis) for the transmission of the directions of one, two, or three axes, by a single quantum carrier.