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# Scaling theory for the free-energy barrier to homogeneous nucleation of a non-critical phase near a critical point

## I Introduction

It is rare for a condensed matter system to possess only one phase transition, which raises the question of how neighbouring phase transitions affect each other. There are many possible effects, and here we consider one of them, namely how nucleation associated with one phase transition is affected by the critical point of a second transition. Consider a first-order phase transition, transition $`\alpha `$, which occurs at a temperature $`T_\alpha `$. Above $`T_\alpha `$ the high-temperature phase, call it $`\alpha _{HT}`$, is the equilibrium phase while below it the low-temperature phase, $`\alpha _{LT}`$, is the equilibrium phase. Fig. 1 is a schematic of the temperature axis of the phase diagram. If we cool the high-temperature phase below $`T_\alpha `$ then it ceases to be the equilibrium phase. At some degree of supercooling a nucleus of the low temperature phase will appear and grow into a macroscopic $`\alpha _{LT}`$ phase. The initial step, the formation of a nucleus of the $`\alpha _{LT}`$ phase, is an activated process — a free energy barrier must be surmounted . The rate at which nuclei overcome a barrier of height $`\mathrm{\Delta }F^{}`$ scales as $`\mathrm{exp}(\mathrm{\Delta }F^{}/kT)`$ and so this rate is very sensitive to the barrier height . Here we calculate $`\mathrm{\Delta }F^{}`$ for nucleation near a critical point of another phase transition, which we call transition $`\beta `$. Transition $`\beta `$ is Ising-like. So, we have two phase transitions: a strongly first order phase transition $`\alpha `$, whose dynamics we are studying, and a transition with a critical point, transition $`\beta `$, which lies at a temperature $`T_\beta <T_\alpha `$ and so occurs within the $`\alpha _{HT}`$ phase when it is not the true equilibrium phase. At an Ising critical point the thermodynamic functions contain singular power-law terms with exponents which depend only on dimensionality . Below, we show that $`\mathrm{\Delta }F^{}`$ also contains a singular power-law term with exponents which depend only on dimensionality. The singular part of $`\mathrm{\Delta }F^{}`$ has the same form as that in the order parameter, so for example, it scales with temperature as $`|TT_\beta |^\beta `$, where $`\beta `$ is the usual critical exponent . This singular part means that the derivative of $`\mathrm{\Delta }F^{}`$ with respect to temperature diverges as the critical point is approached: the barrier to nucleation is very sensitive to changes in temperature near the critical point. Which is true for any system with an Ising-like critical point.

The scaling analysis here follows on from mean-field calculations performed by the author , see also Ref. . Which in turn followed on from the pioneering simulations of ten Wolde and Frenkel  who were the first to appreciate that critical fluctuations could reduce $`\mathrm{\Delta }F^{}`$ near the critical point of a metastable fluid-fluid transition. The results of the mean-field calculations are consistent with the scaling analysis here; if we take the equations of the present work and set the exponents to their (incorrect) mean-field values we reproduce the exponents found in Refs. . Finally, see the work of Dixit and Zukoski  for an alternative approach to nucleation near a critical point; one where dynamics are explicitly but approximately included.

Perhaps the easiest systems in which to observe the effects found here, are mixtures of liquids. There nucleation of either the vapour phase or a crystalline phase may occur near the continuation of a line of critical solution temperatures, i.e., near to a critical point of liquid-liquid demixing. A line of critical solution temperatures does not stop when the liquid ceases to be the equilibrium phase but continues into the region where it is metastable with respect to a transition to a vapour or crystalline phase. It is this continuation that affects nucleation.

The study of nucleation near a critical point was sparked by interest in the nucleation of the crystalline phase of globular proteins . At least some globular proteins have a fluid-fluid critical point within the fluid-crystal coexistence region . The fact that the predictions made here are universal is very useful with regard to protein crystallisation as the interactions between protein molecules are generally rather poorly understood, particularly before they have been crystallised and their structure determined . We know that our predictions will apply to nucleation near any fluid-fluid critical point found in a protein solution, without needing to know anything about the protein-protein interactions.

## II Theory for nuclei which couple to the order parameter

We will describe the critical point of transition $`\beta `$ using the standard language of Ising spin systems, although of course our results also apply to critical points in fluids. The order parameter is $`m`$, the temperature $`t=(TT_\beta )/T_\beta `$, and the field is $`h`$ and couples to the order parameter as $`hm`$. The critical point is then at $`t=0`$, $`h=0`$, see Fig. 1. For fluid systems the external field $`h`$ is the chemical potential minus that at coexistence, and $`m`$ is a density difference. We set the lattice spacing to $`a`$. For definiteness we set $`m`$ to be positive in the nucleus. The symmetry between $`+m`$ and $`m`$ means we can do so without loss of generality.

The dynamics of a first-order phase transition starts with nucleation , where a microscopic nucleus of the new phase first appears. The nucleus at the top of the barrier, with the highest free energy $`\mathrm{\Delta }F^{}`$, determines the rate and so we will consider only this nucleus. It is generally called the critical nucleus. Note that conventionally the word critical is used to denote both a continuous transition and the nucleus at the top of the barrier although there is no connection between the two uses of the word. Although this terminology is a little unfortunate we will use it here and so we will be studying a critical nucleus near a critical point.

For nucleation at a strongly first-order phase transition (which transition $`\alpha `$ is assumed to be), the nucleus must contain a compact core of spins near their state in the bulk $`\alpha _{LT}`$ phase, as only in this state do they have a lower free energy than in the $`\alpha _{HT}`$ phase. For all strongly first-order transitions, the free energy will be higher for spins intermediate between the two phases, here $`\alpha _{HT}`$ and $`\alpha _{LT}`$. It is this core which will grow to form the $`\alpha _{LT}`$ phase. See for example Refs.  which discuss the classical theory for nucleation which is based on this observation.

Now, this core of spins will perturb the surrounding spins out to a distance of the correlation length $`\xi `$. Thus, the volume perturbed is of order $`\xi ^d`$ and so diverges as the critical point is approached. $`d`$ is the dimensionality. The volume around the core where $`m`$ is small we term the fringe. As in our earlier mean-field calculations  we split the nucleus into a core and a fringe. This is illustrated schematically in Fig. 2. As $`\alpha `$ is a strongly first-order transition, the order parameter of transition $`\beta `$, $`m`$, in the core will be of order unity, i.e., not small, and therefore far above the values of $`m`$ reached by critical fluctuations. The critical fluctuations will however affect the fringe where $`m`$ is small. We note that the compact core of spins resembles a small colloidal particle in that it is a compact, roughly spherical object, which interacts with and thus perturbs its surroundings. The problem of a colloidal particle in a near critical system has been considered, see Refs. .

The core of the nucleus will be much smaller than the correlation length $`\xi `$ near the critical point as it will be only a few lattice sites across whereas $`\xi `$ diverges . Thus, near the critical point, the core is a point-like perturbation which couples to the order parameter $`m`$. It will couple to $`m`$ unless this is prevented by a symmetry. Point-like perturbations near a critical point are generic — all point-like perturbations to the order parameter $`m`$ perturb large length-scale critical fluctuations in the same way, differing only in a scale factor. Near the critical point where $`\xi a`$, scale invariance implies that any perturbation of size much less than $`\xi `$ must cause a order parameter perturbation of the same form, because all such perturbations are simply interrelated by a change of length-scale. The presence of a nucleus at the origin $`\mathrm{𝟎}`$ must therefore produce (at large distances) the generic perturbation to $`m`$. We define the thermal average excess of $`m(𝐫)`$ due to the presence of a nucleus at the origin as

$$<m_n(𝐫)>=<m(𝐫)>_n<m(𝐫)>,$$
(1)
where $`<m(𝐫)>_n`$ ($`<m(𝐫)>`$) is the thermal average value of $`m(𝐫)`$ when there is (is not) a nucleus at the origin. Compare this to the 2-point correlation function, $`G(𝐫)`$, for the order parameter, defined by

$$G(𝐫)=<m(\mathrm{𝟎})m(𝐫)><m(\mathrm{𝟎})><m(𝐫)>.$$
(2)
Note that $`G(𝐫)`$ is the thermal average of $`m(𝐫)`$ if $`m(\mathrm{𝟎})`$ is fixed to 1. As a point perturbation is generic for the fluctuations on length scales $`a`$, the function $`<m_n(𝐫)>`$ can only differ from $`G(𝐫)`$ by a scale factor when $`ra`$. Calling this scale factor $`C`$,

$$<m_n(𝐫)>=CG(𝐫)ra.$$
(3)
$`C`$ will depend on the properties of the core. This result has been found before not for a nucleus but for a small colloidal particle immersed in a near-critical fluid . Defining the total excess of $`m`$ due to the presence of the critical nucleus as $`m^{}`$, we have

$`m^{}={\displaystyle d𝐫<m_n(𝐫)>}.`$ (4)
Splitting the integration at $`r_c`$ which satisfies $`ar_c\xi `$, and using Eq. (3) for the integrand of the integral for $`r>r_c`$ we have

$$m^{}=_{r<r_c}d𝐫<m_n(𝐫)>+C_{r>r_c}d𝐫G(𝐫).$$
(5)
Now, the response function $`\chi `$ is equal to the integral over $`G(𝐫)`$

$$d𝐫G(𝐫)=\chi ,$$
(6)
and it contains a leading order singular part $`\chi _S`$ coming from fluctuations on a length-scale of the correlation length $`\xi `$, and so coming from those parts of the integral where $`r=O(\xi )`$. Thus the second integral of Eq. (5) for $`m^{}`$ contains $`\chi _S`$: $`m^{}`$ is singular at the critical point. Near the critical point $`\chi _S`$ dominates $`\chi `$ and so the term $`C\chi _S`$ in the second integral of Eq. (5) will dominate $`m^{}`$. Thus, we have for the leading order singularity in $`m^{}`$, $`m_S^{}`$,

$$m_S^{}=C\chi _S=C|t|^\gamma X_\pm (h/|t|^{\beta \delta }),$$
(7)
where $`X_\pm `$ are scaling functions, and $`\gamma `$, $`\beta `$ and $`\delta `$ are critical exponents. $`X_+`$ is the scaling function above the transition, $`t0`$, while $`X_{}`$ is the scaling function below the transition, $`t0`$. The second equality is obtained by substituting the standard scaling expression for $`\chi _S`$ . Close to the critical point, the total order parameter excess associated with the nucleus, $`m^{}`$, diverges with the precisely the same scaling behaviour as the order parameter response function, $`\chi `$.

Having determined the size of the nucleus, we wish to know its free energy. We start by splitting the free energy barrier into a nonsingular part $`\mathrm{\Delta }F_{NS}`$ plus a leading order singular part $`\mathrm{\Delta }F^{}`$,

$$\mathrm{\Delta }F^{}=\mathrm{\Delta }F_{NS}^{}+\mathrm{\Delta }F_S^{}$$
(8)
The leading order singular part, $`\mathrm{\Delta }F_S^{}`$, of $`\mathrm{\Delta }F^{}`$, is expected to have the usual scaling form, of a power of $`|t|`$ times a function of $`h/|t|^{\beta \delta }`$,

$$\mathrm{\Delta }F_S^{}=|t|^xY_\pm (h/|t|^{\beta \delta }),$$
(9)
with $`x`$ an as yet unknown exponent. To determine $`x`$ we note that the derivative of the free energy of the system $`F`$ with respect to $`h`$ is,

$$\frac{F}{h}=M,$$
(10)
where $`M`$ is the total order parameter $`m`$ of the system. Thus, as $`\mathrm{\Delta }F^{}`$ is the free energy with a nucleus at the origin minus that without a nucleus at the origin, then the derivative of $`\mathrm{\Delta }F^{}`$ with respect to $`h`$ is simply the negative of the total order parameter with a nucleus minus that without a nucleus ,

$$\frac{\mathrm{\Delta }F^{}}{h}=m^{}.$$
(11)
This is for the complete $`\mathrm{\Delta }F^{}`$. The leading-order singular term in $`\mathrm{\Delta }F^{}`$, denoted by $`\mathrm{\Delta }F_S^{}`$, will yield minus the leading-order singular term in $`m^{}`$, upon differentiation with respect to $`h`$

$$\frac{\mathrm{\Delta }F_S^{}}{h}=m_S^{}.$$
(12)
The derivative with respect to $`h`$ of scaling functions like $`Y_\pm (h/|t|^{\beta \delta })`$, brings an additional $`|t|^{\beta \delta }`$ factor. Thus for Eqs. (9) and (12) to yield the correct exponent $`\gamma `$ for $`m^{}`$ we require that $`x\beta \delta =\gamma `$. Using the relation between exponents $`\beta \delta =\beta +\gamma `$  we obtain $`x=\beta `$. So, setting $`x=\beta `$ in Eq. (9) we obtain

$$\mathrm{\Delta }F_S^{}=|t|^\beta Y_\pm (h/|t|^{\beta \delta }),$$
(13)
the singular part of the free energy scales with the same exponent, $`\beta `$, as the bulk order parameter. This is for Ising-like systems but we expect that analogous singular terms will be found near critical points of transitions with order parameters which are not scalars, for example in the Heisenberg model where the order parameter is a three-dimensional vector.

As $`\beta >0`$, $`\mathrm{\Delta }F_S^{}=0`$ at the critical point, and so the universal singular part is zero. The free energy barrier $`\mathrm{\Delta }F^{}`$ at the critical point is equal to some non-universal value. However, as $`\beta <1`$, the derivative of $`\mathrm{\Delta }F^{}`$ with respect to temperature diverges as $`|t|^{\beta 1}`$ as the critical point is approached at $`h=0`$. The signs of the divergences as the critical point is approached from above and below are those of $`Y_\pm (0)`$ which are unknown. However, on physical grounds we might expect critical fluctuations to reduce the barrier to nucleation, and this is what is found in the mean-field theory calculations for $`T>T_\beta `$ of Ref. , i.e., within mean-field theory it has been found that $`Y_+(0)>0`$. If $`Y_\pm (0)`$ are both positive, then at fixed $`h=0`$, the free energy barrier will have a local minimum at $`T=T_\beta `$. As the derivative of $`\mathrm{\Delta }F_S^{}`$ diverges, near the critical point the variation in $`\mathrm{\Delta }F^{}`$ is dominated by that in $`\mathrm{\Delta }F_S^{}`$, and so if $`\mathrm{\Delta }F_S^{}`$ has a minimum at the critical point so does $`\mathrm{\Delta }F^{}`$.

Along the critical isotherm,

$$\mathrm{\Delta }F_S^{}=\mathrm{\Sigma }\text{sgn}(h)|h|^{1/\delta }t=0,$$
(14)
where $`\mathrm{\Sigma }`$ is an amplitude and the scaling with $`h`$ is fixed by the requirement that it be the same as that of $`m`$. From Eq. (12) we see that as $`m_S^{}>0`$ then the $`h`$ derivative of $`\mathrm{\Delta }F_S^{}`$ must be negative. For this to be true we must have that $`\mathrm{\Sigma }<0`$. Note that $`m_S^{}>0`$ because we set $`m`$ in the core to be $`>0`$, if the nucleating phase has instead $`m<0`$, then in that case $`\mathrm{\Sigma }>0`$. $`\mathrm{\Sigma }`$ is a function not only of the properties of the critical system but of the nucleating phase. At the critical point the rate of decrease of $`\mathrm{\Delta }F^{}`$ ($`=m^{}`$) diverges, so near the critical point the nucleation barrier is a rapidly decreasing function of $`h`$.

### A Critical amplitude ratios

In the $`h=0`$ limit, the scaling functions $`X_\pm `$ of $`\chi _S`$, Eq. (7), simplify

$`\chi _S`$ $`=`$ $`\mathrm{\Gamma }_\pm |t|^\gamma h=0,`$ (15)
where $`\mathrm{\Gamma }_\pm =X_\pm (0)`$. $`\mathrm{\Gamma }_\pm `$ are critical amplitudes, and are non-universal. However, the critical amplitude ratio $`\mathrm{\Gamma }_+/\mathrm{\Gamma }_{}`$ is universal . The fact that not only the exponents but the critical amplitude ratios are universal means that we can even make a universal prediction about the ratio of the size of the nucleus just above the critical point to that just below. If we take the ratio $`m_S^{}(+|t|)/m_S^{}(|t|)`$, we see, using Eq. (15), that

$$\frac{m_S^{}(+|t|)}{m_S^{}(|t|)}=\frac{\mathrm{\Gamma }_+}{\mathrm{\Gamma }_{}}h=0,$$
(16)
which is universal. As near the critical point $`m_S^{}`$ dominates $`m^{}`$, we have that near the critical point: 1) the excess magnetisation associated with the nucleus is the same in each of the two coexisting phases at some $`t<0`$, and 2) that the ratio of $`m^{}`$ at $`|t|`$ to the common value of the excess $`m`$ in the coexisting phases at $`|t|`$ is universal. In three dimensions $`\mathrm{\Gamma }_+/\mathrm{\Gamma }_{}=4.9`$  so the nucleus is approximately five times bigger $`|t|`$ above the transition than $`|t|`$ below. Via the nucleation theorem  it is possible to estimate the size of the critical nucleus. Thus measurements on nucleation rates can potentially be used to estimate not only critical exponents but critical amplitude ratios.

## III Dynamic scaling for the equilibration time near $`T_\beta `$

Now, the singular part of the barrier, $`\mathrm{\Delta }F_S^{}`$, is universal because it originates in long wavelength fluctuations, fluctuations with wavelengths $`a`$, where the microscopic details of the system are irrelevant. However, these long wavelength fluctuations are slow, firstly as a direct consequence of them having a long wavelength (this applies if $`m`$ is a conserved variable ), and secondly because as the critical point is approached the free energy becomes a very flat function of the order parameter which reduces the driving force which relaxes fluctuations. Dynamic scaling theory yields for the characteristic relaxation time $`\tau _R`$ (=$`2\pi `$ over the characteristic frequency) of a small wavevector mode, $`k<<a^1`$, near a critical point

$$\tau _R=k^zD_\pm (k\xi ,h/|t|^{\beta \delta }),$$
(17)
the relaxation time of a mode of wavevector $`k`$ at temperature $`t`$ and field $`h`$. The exponent $`z`$ is a dynamic scaling exponent. Dynamic scaling exponents depend not only on the symmetry of the order parameter and the dimensionality as the static exponents, $`\beta `$, $`\gamma `$, etc. do, but also on whether the order parameter $`m`$ is conserved or not. If $`m`$ is the magnetisation then it can vary locally without transport of $`m`$ and so it is non-conserved, but if $`m`$ is a density difference then as the total number of molecules is conserved it cannot vary in a volume of space without transport in or out of that volume, so it is then a conserved variable. In either case $`z`$ is positive. Assuming that fluctuations with wavelengths larger than the correlation length can be ignored we have that at a given $`t`$ and $`h`$, the longest relevant relaxation time is that of a mode of wavevector $`k=2\pi /\xi `$. Calling the relaxation time of this mode $`\tau _\xi `$ we have, from Eq. (17),

$`\tau _\xi `$ $`=`$ $`\xi ^z(2\pi )^zD_\pm (2\pi ,0)`$ (18)
$`\tau _\xi `$ $`=`$ $`\tau _\pm |t|^{z\nu }h=0,`$ (19)
where we have set $`h=0`$ for simplicity, the generalisation to non-zero fields is easy. The second line used the scaling for the correlation length $`\xi =\xi _\pm |t|^\nu `$ for $`h=0`$, and the amplitudes $`\tau _\pm =\xi _\pm ^z(2\pi )^zD_\pm (2\pi ,0)`$.

Our expression for the free energy barrier to nucleation, Eq. (8), includes a singular part $`\mathrm{\Delta }F_S^{}`$ coming from long-wavelength fluctuations. This singular part is an equilibrium quantity: it is the free energy change of equilibrium fluctuations due to the nucleus. Note that here by equilibrium we mean that the fluctuations in $`m`$ etc. have relaxed to equilibrium, the system is not at true equilibrium as it is in the $`\alpha _{HT}`$ phase below $`T_\alpha `$. Thus, our expression for the free energy barrier, Eq. (8), is only meaningful once a time much larger than $`\tau _\xi `$ has elapsed at that temperature and so the fluctuations in $`m`$ have equilibrated.

However, $`\tau _\xi `$ diverges as the critical point is approached so the nearer we are to the critical point the longer we have to wait before Eq. (8) gives the correct barrier to nucleation. For $`m`$ conserved, $`z=4\eta `$ and so putting in the values for $`\eta `$ and $`\nu `$ we have that $`\tau _\xi `$ scales as $`|t|^{2.5}`$: it diverges rather rapidly as the critical point is approached. For $`m`$ not conserved, $`z`$ is close to 2 and so putting in the values for $`\eta `$ and $`\nu `$ we have that $`\tau _\xi `$ scales as $`|t|^{1.3}`$: it still diverges but more slowly. So, the closer the critical point is approached the longer is the waiting time before our expressions for the nucleation barrier, and size of the nucleus are valid. This, together with the effect of gravity on long wavelength fluctuations will limit how closely the critical point can be approached and the behaviour predicted by Eqs. (7) and (8) observed.

## IV Nuclei which do not couple to the order parameter and non-Ising universality classes

Section II considered the case of a nucleus near an Ising-like transition, and in which the nucleus couples to the order parameter. In this section we start by considering nuclei near an Ising-like critical point which do not couple to the order parameter, and then move on to consider critical points in other universality classes. There are results for colloidal particles in fluids near Ising-like critical points where the particles do not couple to the order parameter . This is so when the two phases which form below $`T_\beta `$ are related by symmetry and the nucleus does not discriminate between these two phases. Now, whether or not a nucleus (or colloidal particle) couples to the order parameter, it will in general couple to the energy density $`u`$. The perturbation to the energy density around a particle/nucleus is given by the energy correlation function. A scaling argument analogous to that in the previous section can be constructed to yield the result that the coupling to the energy density yields a singular part in the free-energy barrier which scales as the energy density $`u`$, i.e.,

$$\mathrm{\Delta }F_S^{}=|t|^{1\alpha }Z_\pm (h/|t|^{\beta \delta }),$$
(20)
where $`\alpha `$ is the specific-heat exponent, and $`Z_\pm `$ are scaling functions. The right-hand side of Eq. (20) is the appropriate scaling for the energy density. Now, $`1\alpha >\beta `$, and so if a nucleus couples to both $`m`$ and $`u`$ then the singular term from the $`m`$ coupling, Eq. (13), will dominate and we can neglect the singularity of Eq. (20): we did this in the previous section. In general, we always expect the nucleus to couple to the energy density but the resulting singularity, Eq. (20) will be dominated by that from the $`m`$ coupling unless the latter is absent in which case Eq. (20) should give the dominant singularity in the free energy barrier to nucleation. Note that the temperature derivative of the nucleation barrier $`\mathrm{\Delta }F^{}/T`$. varies as the heat capacity, i.e., as $`|t|^\alpha `$ at $`h=0`$.

So, for a nucleus which does not couple to the order parameter, we still have a singularity in the free-energy barrier, Eq. (20), but it is weak. In three dimensions, $`\alpha =0.11`$ and so the temperature derivative of the free-energy barrier diverges only as $`|t|^{0.11}`$ at $`h=0`$: this weak divergence may be difficult to observe. Also, at $`h=0`$, if the nucleus does not couple to $`m`$, then $`m^{}=0`$ at $`h=0`$ by symmetry. Thus, Eq. (11), the field derivative of $`\mathrm{\Delta }F^{}/h=0`$ at $`h=0`$.

As mentioned in the introduction, in fluid systems like protein solutions and liquid mixtures, there is no symmetry available to prevent the coupling of the nucleus to $`m`$. So the results of the previous section apply there, and the coupling to the energy density is subdominant. However, let us consider systems in universality classes other than that of the Ising model. We speculate that our finding of singular terms in the free-energy barrier to nucleation near a critical point is not restricted to systems with a scalar order parameter. Even if the order parameter is, say a two-dimensional unit vector as it is in the universality class of the XY-model , then the nucleus of a new phase should couple to the critical fluctuations. For example, the fluid to superfluid transition in liquid <sup>4</sup>He is in the XY universality class. Now, the vector order parameter is the phase of a wavefunction and a nucleus of another phase, e.g., the vapour phase, will not couple to the phase of a quantum mechanical wavefunction: $`\mathrm{\Delta }F^{}`$ does not depend on the local phase of the wavefunction. However, there is no reason for the nucleus not to couple to energy fluctuations near the fluid to superfluid transition. If it does so then $`\mathrm{\Delta }F^{}`$ will contain a singular term of the form of Eq. (20).

The fluid to superfluid transition crosses the liquid-vapour transition , and so nucleation of the vapour phase can occur near the continuation of the superfluid-fluid transition into conditions of pressure and temperature such that the vapour phase is the equilibrium phase. However, for the XY model in three dimensions, $`\alpha `$ is (very small but) negative which means the heat capacity, and thus the temperature derivative of $`\mathrm{\Delta }F^{}`$, has a cusp only: it does not diverge. This may make proving or disproving our speculation difficult.

## V Conclusion

We have considered the effect of a critical point on the nucleation of a new phase of another phase transition. The order parameter associated with the critical point is a scalar, putting the transition in the universality class of the Ising model. The critical point results in power-law singularities in both the free energy barrier to nucleation, $`\mathrm{\Delta }F^{}`$, and the size of the nucleus, $`m^{}`$. The singular term in $`\mathrm{\Delta }F^{}`$ has the same scaling as the order parameter, and that in $`m^{}`$ has the scaling of the response function of the order parameter. Thus, for example, as the critical point is approached at zero field, the singular term in $`\mathrm{\Delta }F^{}`$ varies as $`|t|^\beta `$, where $`\beta `$ is the usual critical exponent and $`t`$ is the temperature minus that at the critical point. As $`\beta >0`$, the singular term in the free energy barrier tends to zero as the critical point is approached. However, derivatives of $`\mathrm{\Delta }F^{}`$, both with respect to the temperature and to the external field, diverge as the critical point is approached: the free-energy barrier to nucleation varies rapidly near the critical point. These predictions are universal, they apply to nucleation in any system in which nucleation of a new phase occurs near a critical point in the universality class of the Ising model.

All the above holds given only that the core of the nucleus, where the nucleus resembles the new bulk phase that is nucleating, couples to the order parameter. It will do so unless prevented by a symmetry. This symmetry is clearly absent in fluid systems, in which the order parameter is a density and/or composition difference. In the previous section we speculated that there are also singular terms in $`\mathrm{\Delta }F^{}`$ near critical points in other universality classes. In other universality classes it is clear that symmetry can prevent coupling to the order parameter, in which case the singularity in $`\mathrm{\Delta }F^{}`$ will be weaker.

The relaxation time diverges as the critical point is approached, see section III. Thus, in experiment there is a limit to how close the critical point can be approached before the relaxation time becomes prohibitively long. This may limit the minimum value of $`|t|`$ that is achievable or it may be limited by some other factor. For example, the protein lysozyme has a fluid-fluid transition with a critical point within the fluid-crystal coexistence region , and thus is a candidate for studying nucleation of a non-critical phase, here a crystalline phase, near an Ising-like critical point. Far from the critical point the characteristic relaxation time can be estimated as the time a lysozyme molecules takes to diffuse its own diameter. The single particle diffusion constant of lysozyme $`D=O(10^{10}\text{m}^2\text{s})`$ , and its diameter is approximately 4nm . This gives a relaxation time of order $`10^7`$s. Using this as the order of magnitude of the amplitudes $`\tau _\pm `$, we have that at $`h=0`$, the relaxation time $`\tau _\xi `$ is of order $`10^7|t|^{2.5}`$s at a temperature $`t`$. The exponent of $`t`$ is $`z\nu `$, with $`z`$ taking its value for a conserved order parameter. Now, assuming careful temperature control the critical temperature can be approached to within, say, $`0.1^{}`$C. As the effective interactions between the molecules in solution vary strongly with temperature $`0.1^{}`$C should correspond to $`|t|=O(10^210^3)`$, not $`|t|=4\times 10^4`$ as it would for temperature independent interactions. At $`|t|=10^3`$, we have a relaxation time $`\tau _\xi =O(1\text{s})`$: still rather short. Thus, in experiments on globular protein molecules like lysozyme, limitations on how well the temperature can be controlled are the limiting factor; the relaxation time $`\tau _\xi `$ is always well within the range accessible in experiment.

It is a pleasure to acknowledge discussions with R. Evans, A. Parry and P. Upton. This work was supported by EPSRC (GR/N36981).


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# Fluctuations of the correlation dimension at metal-insulator transitions

\[

## Abstract

We investigate numerically the inverse participation ratio, $`P_2`$, of the 3D Anderson model and of the power-law random banded matrix (PRBM) model at criticality. We found that the variance of $`\mathrm{ln}P_2`$ scales with system size $`L`$ as $`\sigma ^2(L)=\sigma ^2(\mathrm{})AL^{D_2/2d}`$, being $`D_2`$ the correlation dimension and $`d`$ the system dimension. Therefore the concept of a correlation dimension is well defined in the two models considered. The 3D Anderson transition and the PRBM transition for $`b=0.3`$ (see the text for the definition of $`b`$) are fairly similar with respect to all critical magnitudes studied.

\]

Critical eigenfunctions at metal-insulator transitions show multifractality, whose study has been very intensive in the last two decades . Each critical eigenfunction $`\varphi _\alpha (𝐫)`$ can be characterized by a set of inverse participation ratios (IPR)

$$P_q^{(\alpha )}=|\varphi _\alpha (𝐫)|^{2q}d^dr,$$
(1)
where the index $`\alpha `$ label the different eigenfunctions and $`d`$ is the embedding dimension. In a good metal the IPR scale with size $`L`$ as $`P_q^{(\alpha )}L^{d(q1)}`$, while in an insulator $`P_q^{(\alpha )}L^0`$. Wegner found, from a renormalization-group treatment of the metal-insulator transition in $`2+ϵ`$ dimensions, that the average IPR at criticality show an anomalous scaling of the form

$$P_qL^{D_q(q1)},$$
(2)
being $`D_q`$ a set of generalized fractal dimensions.

The IPR fluctuations were studied for 2D systems in the framework of the supersymmetry method and it was found that the distribution function of $`P_q^{(\alpha )}`$ normalized to its typical value $`P_2^{(\mathrm{typ})}`$ is scale invariant at criticality and inversely proportional to the squared adimensional conductance . Although the 2D case does not present a true Anderson transition, the previous result motivated the conjecture that in general the distribution function of $`P_q^{(\alpha )}`$ normalized to its typical value, is universal, i.e., size independent for $`L\mathrm{}`$. Accordingly, it is assumed that the distribution function of $`\mathrm{ln}P_q^{(\alpha )}`$ is a universal curve which is just horizontally shifted by changes in $`L`$.

Recently it was claimed by Parshin and Schober , on the basis of numerical calculations, that the correlation dimension $`D_2`$ in the 3D Anderson model at criticality is not well-defined due to strong fluctuations in the IPR. For the sizes considered, it seemed that the standard deviation of the distribution of $`\mathrm{ln}P_2^{(\alpha )}`$ grows with system size proportionally to $`\mathrm{ln}L`$. Then, for $`L\mathrm{}`$ the correlation dimension, instead of tending to a single value, it would tend to a universal distribution.

If confirmed, the previous result would impose drastic changes in our understanding of critical properties at metal-insulator transitions. Mirlin and Evers  addressed this problem and study theoretically and numerically the fractal properties of the power-law random banded matrix (PRBM) model at criticality. They found the distribution function of the IPR to be scale independent for all the values of the parameter $`b`$ characterizing this model (see below). The model describes a whole family of critical theories parameterized by $`b`$, in the same way as the dimensionality labels the different Anderson transitions. The standard 3D Anderson transition should be equivalent to a PRBM model with a $`b`$ of the order of unity, although this belief is not based on any direct knowledge. They finally claimed that the disagreement between their results and those of Ref.  is due to the small system sizes used in  and not to the different models employed.

Our aim is to perform a careful statistical analysis on the data from numerical calculations of both the 3D Anderson model and the PRBM model at criticality using system sizes larger than in previous calculations . We want to study the system size dependence of the fluctuations of the IPR and to elucidate: i) whether the correlation dimension at the Anderson transition is well-defined or alternatively presents an scale invariant distribution, ii) whether this transition is equivalent or not to a PRBM model at criticality.

We first consider the standard Anderson model on a 3D simple cubic lattice, represented by a tight-binding Hamiltonian with matrix elements of the form

$$H_{ij}=ϵ_i\delta _{ij}+t_{ij},$$
(3)
where $`i,j`$ denote lattice sites. The diagonal (site) energies are randomly distributed with constant probability in the interval $`W/2<ϵ_i<W/2`$, and the off-diagonal elements $`t_{ij}`$ are taken equal to unity for nearest neighbors, which sets the energy scale, and to zero otherwise.

The PRBM model, introduced in Ref. , describes a 1D sample with random long-range hopping. It can approximately represent a variety of physical systems from an integrable billiard with a Coulomb scattering center , to the Luttinger liquid at finite temperatures . The model is represented by real symmetric matrices whose entries are randomly drawn from a normal distribution with zero mean and a variance depending on the distance of the matrix element from the diagonal

$$(H_{ij})^2=\frac{1}{1+(|ij|/b)^{2\alpha }}.$$
(4)
This model was shown to undergo a sharp transition at $`\alpha =1`$ from localized states for $`\alpha >1`$ to delocalized states for $`\alpha <1`$. This transition is supposed to be similar to an Anderson metal-insulator transition, presenting multifractality of eigenfunctions and non-trivial spectral compressibility at criticality. The parameter $`b`$ determines the critical dimensionless conductance and so establishes the character of the transition. For $`b=1`$ the nearest level spacing distribution differs from the typical one at the 3D Anderson metal-insulator transition . Recent calculations by us have obtained different diverging exponent for the correlation length as the transition is approached from below and from above .

We obtain the eigenfunctions and eigenvalues of the Hamiltonian matrix by numerical diagonalization. In the case of the Anderson model, we use techniques for large sparse matrices, in particular a Lanczos tridiagonalization without reorthogonalization method , while for the PRBM case we employ standard diagonalization subroutines, since we have to deal with full matrices. For the Anderson model, the system size varies between 5 and 40, and we consider a small energy window $`(1,1)`$ around the center of the band. We take for the critical disorder the value $`W_\mathrm{c}=16.5`$. In the PRBM case, the system size ranges between $`L=100`$ and 15000 and the energy window considered is $`(0.4,0.4)`$. Reducing the width of the previous windows do not alter the results. The number of random realizations is such that the number of states included for each $`L`$ is roughly equal to $`3\times 10^5`$, except for $`L=40`$ in the Anderson model where this number is $`2\times 10^4`$. In order to reduce edge effects, we use periodic boundary conditions in all cases considered.

To elucidate whether the correlation dimension $`D_2`$ possesses a well defined single value or alternatively corresponds to a distribution, we have calculated the IPR for the wavefunctions in the energy window considered for many disorder realizations. For each $`L`$ we obtain the distribution function of $`\mathrm{ln}P_2^{(\alpha )}`$, since this is a well behaved self-averaging magnitude. At the end of the paper, we will also discuss the distribution of $`P_2^{(\alpha )}`$. In Fig. 1 we show the evolution of the distribution function $`F(\mathrm{ln}P_2^{(\alpha )})`$ with $`L`$ for the 3D Anderson model. The system sizes drawn are $`L=5`$, 6, 8, 10, 12, 15, 17, 20, 25, 30 and 40, from right to left. It is clear that $`F(\mathrm{ln}P_2^{(\alpha )})`$ changes with size. As $`L`$ increases this distribution becomes wider and the height of its peak smaller. This is in qualitative, but

not quantitative, agreement with the results of Ref. .

We characterize the previous distribution by its average value, $`\mathrm{ln}P_2^{(\alpha )}`$, and its variance, $`\sigma ^2(L)=\mathrm{var}(\mathrm{ln}P_2^{(\alpha )})`$. This variance increases with $`L`$ and seems to saturate at a constant value, as one can implicitly appreciate from the peak of the distributions. We try a fit of the form

$$\sigma ^2(L)=\sigma ^2(\mathrm{})AL^\gamma ,$$
(5)
with $`\sigma ^2(\mathrm{})`$, $`A`$ and $`\gamma `$ being three adjustable parameters. We found that the exponent $`\gamma `$ was always very close to the correlation dimension divided by $`2d`$. Thus, we fix

$$\gamma =\frac{D_2}{2d},$$
(6)
and keep only two free parameters. In the language of scaling theory, this exponent characterizes the behavior of the irrelevant length. Our assumption that the irrelevant exponent $`\gamma `$ is equal to $`D_2/2d`$ properly interpolates between two known limiting cases of the PRBM model. For $`b1`$, one can get from Eqs. (5) and (6) the $`b\mathrm{ln}L`$ correction predicted in . Similarly, for $`b1`$, the exponent $`\gamma `$ in Eq. (6) tends to $`1/2`$, which implicitly coincides with the results of Ref.  for this regime.

In Fig. 2 we represent on a log-log scale $`\sigma ^2(\mathrm{})\sigma ^2(L)`$ as a function of $`L`$ for the 3D Anderson transition. The fitted values of the free parameters are $`\sigma ^2(\mathrm{})=1.09`$ and $`A=1.24`$. The slope of the straight line has not been fitted and corresponds to $`D_2/2d`$, where $`D_2=1.4`$ has been obtained from the inset of Fig. 2. In this inset we plot $`\mathrm{ln}P_2^{(\alpha )}`$ versus $`\mathrm{ln}L`$. The straight line is a linear fit to the data and its slope is equal to $`D_2`$. The value $`\sigma ^2(\mathrm{})=1.09`$ found is in good agreement with the conjecture $`\sigma ^2(\mathrm{})1`$ .

These results are in contradiction with those of Parshin and Schober , who found a linear increase of $`\sigma (L)`$ with $`\mathrm{ln}L`$. We have checked that $`\sigma (L)`$ versus $`\mathrm{ln}L`$ do not follow a linear behavior. We believe that the disagreement is due to two reasons. Firstly, the relatively small system sizes employed in Ref. , and secondly the use of different estimates of an effective IPR, instead of directly studying the width of the $`\mathrm{ln}P_2^{(\alpha )}`$ distribution. On the other hand, Mirlin and Evers  already obtained for the PRBM model similar results to ours.

Eq. (6) may be also valid for other transitions, like the integer quantum Hall transition, where the irrelevant exponent $`y`$ –which is the same as our $`\gamma `$– is known to be $`y=0.4\pm 0.1`$ and $`D_2=1.48`$. These values are consistent with Eq. (6). Polyakov  and Evers and Brenig  already obtained a relation between the irrelevant exponent $`y`$ and the correlation dimension $`D_2`$, but our result seems to fit more naturally the reported values of $`y`$.

Although $`D_2`$ is well defined in the macroscopic limit, it is clear from Fig. 2 that the results of numerical calculations with present computers will drastically depend on the particular definition of correlation dimension adopted. For the sizes available the distributions of $`\mathrm{ln}P_2^{(\alpha )}`$ are so wide that one can obtain very different numerical values of $`D_2`$ depending on the method of calculation, as pointed out in Ref. , but this does not imply at all the existence of a distribution of correlation dimensions in the macroscopic limit.

We have now performed similar calculations for the PRBM model, considering several values of the parameter $`b`$ in the range where the transition could be similar

to the 3D Anderson transition. As regards the IPR fluctuations, the results for the PRBM model follow the same behavior, given by Eq. (5), as the Anderson transition. In order to show this, we plot in Fig. 3 the same quantity as in Fig. 2, but for the PBRM model with $`b=0.1`$ (squares) and with $`b=0.3`$ (diamonds). The data in all cases are well fitted by straight lines, whose slopes are equal to $`D_2/2d`$. The fitted parameters for the cases shown in Fig. 3 are $`\sigma ^2(\mathrm{})=0.55`$ and $`A=0.56`$ for $`b=0.1`$, and $`\sigma ^2(\mathrm{})=0.33`$ and $`A=0.35`$ for $`b=0.3`$. The values of $`D_2`$ have been obtained by the same procedure as for the Anderson model and are equal to 0.21 and 0.48 for $`b=0.1`$ and 0.3, respectively. For $`b=1`$, $`\sigma ^2(L)`$ is practically constant, explaining the scale-invariance claim made in Refs. . For $`b>1`$, Eq. (5) is still valid, but $`A`$ changes sign. In other words, now the system approaches the asymptotic value $`\sigma ^2(\mathrm{})`$ from above.

Now we focus on the behavior of the asymptotic value $`\sigma ^2(\mathrm{})`$ as a function of $`b`$, which is summarized in Fig. 4. We were not able to fit all the data (including large values of $`b`$ not shown in the figure) with a simple function. Power laws of $`1/b`$ with different exponents are able to fit extended parts of the curve. For example, the dashed line corresponds to a $`1/b`$ dependence and fits fairly well the intermediate regime, $`b1`$, in which we are most interested. For $`4<b<12`$, the results are in reasonable agreement with the $`1/b^2`$ prediction of Evers and Mirlin , based on the fluctuations of the 2D case and taking into account that the dimensionless conductance is proportional to $`b`$.

The distribution of $`zP_2^{(\alpha )}/P_2^{(\mathrm{typ})}`$, where the typical IPR $`P_2^{(\mathrm{typ})}`$ is chosen as the median of the distribution , is very different from the distribution of $`\mathrm{ln}P_2^{(\alpha )}`$ due

to the their strong asymmetries and long tails. We have studied the size dependence of the variance $`\sigma _z^2`$ of $`z`$. For $`b1`$ we have analytically calculated this dependence using the renormalization group method of Levitov . One combines two blocks of size $`L`$ to form a block of size $`2L`$. Some states are assumed to remain practically unchanged in this process, while others combine to form a more extended state. From the evolution equation describing the behavior of the distribution function, one can obtain $`D_2`$ in terms of the parameters of the model . We extended the procedure to obtain the following equation for the variance

$$\sigma _z^2(2L)=2^{D_2/8}\sigma _z^2(L)+\frac{b}{2}\mathrm{\hspace{0.17em}2}^{2D_2}.$$
(7)
We have checked that for $`b<0.3`$ Eq. (7) fits the variance of $`z`$ fairly well. On the other hand, the numerical calculations for larger values of $`b`$ and for the 3D Anderson transition do not follow this behavior. Eq. (7) predicts a power law approach of $`\sigma _z^2(L)`$ to its asymptotic value with an exponent $`D_2/8`$, in contrast with the exponent $`D_2/2d`$ observed for the variance of $`\mathrm{ln}P_2^{(\alpha )}`$.

We have compared the Anderson model with the PRBM model for several values of $`b`$ through different critical parameters. The case $`b=0.3`$ is very similar to the Anderson transition, presenting practically the same values for all the critical magnitudes studied. The correlation dimension divided by the embedding dimension is equal to $`1.4/3=0.47`$ for the Anderson model and to 0.49 for the PRBM model. Correspondingly, the scaling with system size of the fluctuations of $`\mathrm{ln}P_2^{(\alpha )}`$ is rather similar. The asymptotic value of these fluctuations for the PRBM model is the same as for the Anderson model divided by $`d`$. Also, the normalized variance of the nearest level spacing at criticality , which characterizes the intermediate statistics at the transition , is 0.18 for the Anderson model and 0.19 for the PRBM model with $`b=0.3`$.

Following the comparison between the two models, we have finally analyzed the large values tail of the distribution of $`z`$. Mirlin and Evers  predicted for the PRBM model a power-law tail $`F(z)z^{1x_2}`$, where $`x_2`$ depends on the transition considered. For example, $`x_2`$ is equal to 4.2 for $`b=1`$ and 2.1 for $`b=0.3`$. We have checked that this prediction is also obeyed by the Anderson model, for which we obtained a value of $`x_2`$ equal to 1.6, in relative agreement with the PRBM model for $`b=0.3`$.

In summary, we found that the variance of the fluctuations of $`\mathrm{ln}P_2^{(\alpha )}`$ tends to an asymptotic value, implying a well-defined correlation dimension. For the intermediate regime of the PRBM model, $`\sigma ^2(\mathrm{})`$ is proportional to $`1/b`$. For the Anderson transition and the PRBM model at criticality, the variance tends to its asymptotic value as a power law $`L^{D_2/2d}`$. Thus, the irrelevant length scale diverges with an exponent $`D_2/2d`$, a result that may be extended to other transitions like the integer quantum Hall transition. The behavior of the distributions of $`\mathrm{ln}P_2^{(\alpha )}`$ and of $`P_2^{(\alpha )}/P_2^{(\mathrm{typ})}`$ is different. We checked that the 3D Anderson transition and the PRBM transition for $`b=0.3`$ are similar for all the critical magnitudes analyzed: the correlation dimension, the scaling of the fluctuations of $`\mathrm{ln}P_2^{(\alpha )}`$, the exponent characterizing the long $`z`$ tail of the distribution $`F(z)`$ and the normalized nearest level variance.

We would like to thank I.V. Lerner and A. Mirlin for useful discussions, and the Spanish DGESIC, project numbers 1FD97-1358 and BFM2000-1059, for financial support.


text:
# The primordial curvature perturbation in the ekpyrotic Universe

### Introduction

In the ekpyrotic Universe  (called in a slightly different version  the pyrotechnic Universe) the Big Bang originates when a brane moving in an extra dimension collides with a fixed one. Except around the time of the collision, the extra dimension can be integrated out to give a four-dimensional field theory with Einstein gravity and flat space. Before the collision, the Universe is collapsing, with the energy density provided by the field $`\varphi `$ which defines the position of the moving brane. In this phase the Hubble parameter $`H`$, the energy density $`\rho `$ and the negative potential $`V`$ are related by the Friedmann equation

$$\rho =3M_\mathrm{P}^2H^2=\frac{1}{2}\dot{\varphi }^2+V(\varphi ).$$
(1)
The Universe is supposed initially to be almost static with negligible energy density. The energy density increases as the Universe collapses, while remaining negligible compared with the potential. When the moving brane collides with the stationary one, the energy density is converted to radiation, and at the same time the Universe starts to expand.

This ekpyrotic scenario is similar to the pre-big-bang scenario . In both cases the 4-D field theory breaks down at the bounce, whose description would in principle require a string theory calculation (though the calculation may be more tractable in the ekpyrotic case since the bounce can take place far below the string scale). The main difference is that in the pre-big-bang scenario the scalar fields responsible for the energy density during collapse are supposed to have negligible potential.

The adiabatic density perturbation responsible for structure in the Universe is conveniently characterized by the curvature perturbation $``$ seen by comoving observers . Its spectrum $`𝒫_{}`$ must be practically scale-independent (flat). A flat spectrum is generated during inflation with a sufficiently flat potential, and existing calculations  seem to indicate that it is also generated during ekpyrotic collapse provided that the potential has a string-inspired exponential form,

$$V=V_0\mathrm{exp}\left(\sqrt{\frac{2}{p}}\frac{\varphi }{M_\mathrm{P}}\right).$$
(2)
(In , the potential was actually taken to be an exponential function of a field with slightly non-canonical normalization, leading to a slightly scale-dependent spectrum, but for simplicity we focus on the case where the canonically-normalized field appears in the potential.) However, these calculations ignore gravitational back-reaction. In this note we include the back-reaction and obtain a quite different result.

### The unperturbed Universe

The case where the Universe is dominated by a field with an exponential potential has already been studied in the context of power-law inflation . We focus first on the unperturbed case. In addition to the Friedman equation one needs the field equation

$$\ddot{\varphi }+3H\dot{\varphi }+V^{}=0,$$
(3)
or equivalently the relation

$$M_\mathrm{P}^2\dot{H}=\frac{1}{2}\dot{\varphi }^2.$$
(4)
With an exponential potential there is an exact solution of Eqs. (1) and (4), corresponding to

$`a`$ $``$ $`|t|^p`$ (5)
$`H`$ $`=`$ $`p/t`$ (6)
$`{\displaystyle \frac{1}{2}}\dot{\varphi }^2`$ $`=`$ $`{\displaystyle \frac{1}{p}}M_\mathrm{P}^2H^2`$ (7)
$`V`$ $`=`$ $`{\displaystyle \frac{3p1}{p}}M_\mathrm{P}^2H^2.`$ (8)
We will also need the conformal time defined by $`\text{d}\tau =\text{d}t/a`$, which can be taken as

$$\tau =\frac{p}{p1}\frac{1}{aH}.$$
(9)
Choosing $`t>0`$ and $`p>1`$ gives power-law inflation. Choosing $`t<0`$ and $`p=\frac{1}{3}`$ give the pre-big-bang scenario in which there is collapse with no potential. Choosing $`t<0`$ and $`p\frac{1}{3}`$ gives the ekpyrotic scenario in which there is collapse with a dominant potential. As it is hardly more effort we deal with the general case $`0<p<\frac{1}{3}`$ giving collapse with a potential of arbitrary magnitude. In the ekpyrotic case,

$`\rho `$ $``$ $`\dot{\varphi }^2`$ (10)
$`{\displaystyle \frac{1}{2}}\dot{\varphi }^2+V`$ $``$ $`0`$ (11)
$`\ddot{\varphi }+V^{}`$ $``$ $`0`$ (12)
$`a`$ $``$ $`\mathrm{const}.`$ (13)
### The curvature perturbation generated during inflation

Let us first summarize the way in which the vacuum fluctuation of the inflaton field $`\varphi `$ generates the curvature perturbation . Each perturbation $`\delta \varphi `$ with wavenumber $`k/a`$ evolves independently, and using conformal time the quantity $`ua\delta \varphi `$ has the same dynamics as a free field living in flat spacetime, with wavenumber $`k`$ but with some time-dependent mass-squared. Well before horizon exit at $`aH=k`$ the mass is negligible, and at the classical level the perturbation is then supposed to vanish (no particles). There is however a vacuum fluctuation, which after horizon exit becomes a classical gaussian perturbation $`\delta \varphi `$. Evaluated on spatially flat slices, it determines the curvature perturbation $``$ seen by comoving observers ,

$$=H\delta \varphi /\dot{\varphi }.$$
(14)
This quantity is constant during inflation, and on the usual assumption that the pressure perturbation is adiabatic it remains constant until horizon entry. For any sufficiently flat potential the spectrum of $``$ is flat in accordance with observation.

### The calculation ignoring the metric perturbation

Next we summarize the calculation presented in , working therefore with the case $`p0`$ The essential assumption of that calculation is that the metric perturbation may be ignored, leading to111The authors of  use the Guth-Pi-Olson (GPO) formalism  for cosmological perturbations, which however is easily translated to the more standard formalism used here. Indeed, the GPO variable $`S`$ is  $`\frac{2}{3}(k/aH)^2`$ and this quantity immediately after the bounce  (or inflation ) is equated with $`\frac{2}{3}(k/aH)^2H\delta \varphi /\dot{\varphi }`$ evaluated just before the bounce. Comparing with Eq. (14) we see that the $`\delta \varphi `$ of the GPO formalism is evaluated on spatially flat slices. We see also that the use of the GPO formalism requires $``$ to be continuous across the bounce, which in contrast with the case of inflation is a non-trivial assumption.

$$\ddot{\delta \varphi }+[(k/a)^2+V^{\prime \prime }]\delta \varphi =0.$$
(15)
This can be written

$$\ddot{\delta \varphi }+\left(\frac{k^2}{a^2}\frac{2}{t^2}\right)\delta \varphi =0.$$
(16)
We give first a rough argument . The amplification of the quantum fluctuation takes place around the epoch $`(k/a)^2=|V^{\prime \prime }|`$. Indeed, well before this epoch the quantum fluctuation is that of a massless free field in flat spacetime, which on dimensional grounds has the spectrum $`𝒫_\varphi (k/a)^2`$. For an estimate, we take this expression to be valid also at the epoch $`(k/a)^2=|V^{\prime \prime }|`$. Well after this epoch, the negative mass-squared $`V^{\prime \prime }`$ dominates, and $`\delta \varphi `$ increases. In fact, $`\delta \varphi 1/t\dot{\varphi }`$, so that

$$𝒫_\varphi /\dot{\varphi }^2|V^{\prime \prime }/V|=2/pM_\mathrm{P}^2.$$
(17)
This gives $`𝒫_{}(2/p)(H/M_\mathrm{P}^2)^2`$, which when evaluated at reheating is supposed  to give the primordial curvature perturbation for the subsequent hot big bang.

To obtain a more precise result, we go to the quantity $`ua\delta \varphi `$, and conformal time $`\tau `$. Since we are working in the limit $`p0`$ where $`a`$ can be taken to be constant, this change is trivial, Eq. (4) becoming

$$\frac{\text{d}^2u}{\text{d}\tau ^2}+(k^22/\tau ^2)u=0.$$
(18)
This is the same equation as for slow-roll inflation, and using flat spacetime field theory to define the initial condition at $`\tau ^2k^2`$ one finds  at $`\tau ^2k^2`$ a perturbation with spectrum

$$𝒫_u=(2\pi \tau )^2.$$
(19)
In the case of slow-roll inflation, $`\tau =1/(aH)`$ leading to $`𝒫_\varphi =(H/2\pi )^2`$ and

$$𝒫_{}=(H/\dot{\varphi })^2(H/2\pi )^2.$$
(20)
In our case, $`\tau t/a`$ leading to $`𝒫_\varphi =(2\pi t)^2`$ and

$$𝒫_{}=\frac{1}{8\pi ^2p}\left(\frac{H}{M_\mathrm{P}}\right)^2.$$
(21)
### The calculation including the metric perturbation

In the case of slow-roll inflation the metric perturbation is indeed negligible compared with the field perturbation. In general though, they are of the same order. Using the spatially flat slicing, $`ua\delta \varphi `$ satisfies

$$\frac{\text{d}^2u}{\text{d}\tau ^2}+\left(k^2\frac{1}{z}\frac{\text{d}^2z}{\text{d}\tau ^2}\right)u=0,$$
(22)
where

$$z=a\dot{\varphi }/H$$
(23)
For a practically static Universe, $`z\dot{\varphi }`$, which using Eq. (12) gives Eq. (15). For slow-roll inflation, $`za1/\tau `$ giving Eq. (18). In our case, $`zt^p\tau ^{\frac{p}{1p}}`$ giving ,

$$\frac{\text{d}^2u}{\text{d}\tau ^2}+\left(k^2+\frac{p(12p)}{(1p)^2}\tau ^2\right)u=0.$$
(24)
Power-law inflation corresponds to $`p>1`$, giving a negative mass-squared which amplifies the quantum fluctuation . The collapsing case we are considering corresponds to $`0<p<\frac{1}{3}`$, giving a positive mass-squared which does not amplify the quantum fluctuation.

We could obtain an estimate by repeating the previous rough argument, but choose instead to go straight to the precise result. We are interested in the late-time era when $`k^2`$ is negligible, and the spectrum is then

$$𝒫_{}^{}{}_{}{}^{\frac{1}{2}}=\frac{r(p)}{2\pi }\sqrt{\frac{p}{2}}\left(\frac{H}{M_\mathrm{P}}\right)\left(\frac{k}{aH}\right)^{\frac{1}{1p}}.$$
(25)
In contrast with the earlier result Eq. (21), this correctly-calculated quantity is time-independent (because $`at^p`$). In particular,

$$𝒫_{}^{}{}_{}{}^{\frac{1}{2}}=\frac{r(p)}{2\pi }\sqrt{\frac{p}{2}}\left(\frac{H_{\mathrm{reh}}}{M_\mathrm{P}}\right)\left(\frac{k}{a_{\mathrm{reh}}H_{\mathrm{reh}}}\right)^{\frac{1}{1p}}.$$
(26)
On cosmological scales $`k/a_{\mathrm{reh}}H_{\mathrm{reh}}e^N`$ with $`N\text{ }<60`$, the precise value depending on $`H_{\mathrm{reh}}`$ and the subsequent cosmology . The spectral index is

$$n=1+\frac{2}{1p}.$$
(27)
which gives $`n=3`$ for the ekpyrotic case and reproduces the known result $`n=4`$ for the pre-big-bang case.

### The bounce and beyond

We shown that the curvature perturbation during collapse is unviable, but it needs to be evolved to the epoch of horizon entry before one can say that the ekpyrotic (or pre-big-bang) scenario is unviable. The first step it to go across the bounce. The continuity of $``$ is assumed in pre-big-bang discussions and we have seen that it was also assumed in the ekpyrotic scenario . In a separate paper  it is demonstrated that $``$ is indeed continuous in the approximation that the bounce occurs on a unique slice of spacetime. Also, its near-constancy is maintained just after the bounce provided that this slice is smoothly embedded in spacetime.

The validity of these approximations can be ascertained only by a calculation going beyond the 4-D framework. Such a calculation may well violate the assumptions and generate a curvature perturbation, but there is no reason to suppose that its spectrum will be flat. Accepting the validity of the assumptions $``$ will be constant until horizon entry, in contradiction with observation, unless there is either a non-adiabatic pressure perturbation or anisotropic pressure . It may be possible to generate a non-adiabatic pressure perturbation through the vacuum fluctuation of field not contributing significantly to the energy density during collapse, but judging experience with the pre-big-bang case  it will be difficult to make the spectrum of the fluctuation flat. It seems fair to say that, compared with the inflationary scenario, the ekpyrotic and pre-big-bang scenarios are disfavored by the requirement of structure formation.

### Conclusion

In the ekpyrotic scenario the Universe is initially contracting under the influence of an exponential potential. We have shown that the curvature perturbation responsible for the origin of structure is not generated while the Universe is collapsing, and have argued that it is unlikely to be generated subsequently.

As was pointed out in , a simple modification of the ekpyrotic scenario is to generalize the string-inspired potential Eq. (2) by adding a constant to it. One then has an inflation model , which can generate a viable curvature perturbation in the usual way.

## Acknowledgments

I thank Paul Steinhardt, Neil Turok and David Wands for discussions about this subject.


text:
# Electron Fractionalization

## I Spin-Charge Separation in the 1DEG

As far as I know, the idea of electron fractionalization rose out of studies of the one-dimensional electron gas (1DEG). In particular, the idea of spin-charge separation was first explicitly treated by Luther and Emery in the context of a continuum (field theory) limit of the 1DEG. What they showed is that the Hamiltonian can be expressed as a sum

$$H_{1DEG}=H_c[\varphi _c]+H_s[\varphi _s]+H_{irr}[\varphi _c,\varphi _s]$$
(1)
where $`H_c`$ and $`H_s`$ are, respectively, the Hamiltonians which govern the dynamics of the spin and charge fields, $`\varphi _c`$ and $`\varphi _s`$, respectively, and $`H_{irr}`$ (which they did not treat, explicitly) consists of terms that can be neglected in the long wave-length limit (irrelevant terms, in the renormalization group sense). Consequently, as far as the low energy physics is concerned, the spin and charge dynamics are completely decoupled from each other. Moreover, Luther and Emery showed that any space-time electronic correlation function can be expressed as the product of a correlator involving only the spin-fields and one involving only the charge fields.

This work is profound, and although its importance was not widely appreciated at the time, its influence has continued to grow ever since. Under many circumstances, the field theory methods are sufficiently powerful that all relevant correlation functions, even for finite temperature, frequency, or momentum, can be computed explicitly and exactly. In the last couple of years it has even become possible to compute various spectral functions exactly in cases in which the spectrum of either the charge or spin excitations is gapped, so that the bosonized field theory is importantly non-linear.

From a more modern perspective, this body of work concerns itself with the physics of a system at, or in the vicinity of a quantum critical point. An amazing thing about the 1DEG is that, due to the special character of quantum fluctuations in one dimension, there are quantum critical phases, not just critical points. The successfulness of this approach is related to the fact that critical theories are conformally invariant, and conformal invariance in one dimensional quantum or two dimensional classical statistical mechanics turns out to strongly constrain the nature of the correlation functions.

While the thrust of the present discussion concerns the broader implications of electron fractionalization, it is worth noting that in recent years, literal realizations of the 1DEG have become available for experimental study in nanowires, buckeytubes, and edge states in quantum Hall systems.

## II The SSH Model of Solitons in Polyacetylene

The story of the soliton theory of polyacetylene in some sense starts with a beautiful result obtained in the context of relativistic quantum field theories by Jackiw and Rebbi. They noted that in certain field theories, especially in one spatial dimension, one can find solitons with fractional fermion number. However, the subject really got started some years later with the discovery of the conducting polymer, trans-polyacetylene, by Shirakawa, MacDiarmid, and Heeger. (There is no need to review the importance of this discovery here. However, readers who are unfamiliar with polyacetylene are referred to the Fig. 1 and its caption, for an introduction to this polymer.) In thinking about the remarkable properties of polyacetylene, Su, Schrieffer, and Heeger (SSH) (and others) discovered that solitons, which are precisely analogous to those of Jackiw and Rebbi, occur as the lowest energy electronic excitations in the simplest imaginable model (the SSH model) of a set of noninteracting electrons coupled to a lattice deformation (acoustic phonon). Here, however, the solitons have reversed charge-spin relations - they can be neutral with spin 1/2, or if spinless they have charge $`\pm e`$.

Specifically, what SSH showed is that when an electron is added to an otherwise neutral polyacetylene chain, it can break up into two pieces, one of which carries the electron’s charge and the other its spin. This observation bears a clear family relation with the phenomenon of spin-charge separation in the 1DEG discussed above, but it is not identical. In the first place, undoped polyacetylene is a semiconductor, with a moderately large ($`2\mathrm{\Delta }2`$eV) gap, and so is nowhere near being quantum critical. The solitons in polyacetylene are not low energy excitations; the soliton creation energy is approximately $`E_s=2\mathrm{\Delta }/\pi `$. Indeed, spin-charge separation does not occur in the SSH model in the same precise sense as it does in the 1DEG - for instance, there are substantial attractive interactions between the charged and neutral solitons, which lead to a bound-state (a polaron), with a binding energy $`E_p2E_s=(2/\pi )[2\sqrt{2}]\mathrm{\Delta }`$. In other words, spin charge coupling implies that the lowest energy excitation of the system with the quantum numbers of an electron is a quasi-particle with the same quantum numbers as the electron. In this sense, fractionalization is, in fact, a high energy feature of the spectrum of the SSH model. The lowest energy excitation made by adding two electrons to the system is a pair of charged solitons. ( One can understand this effect qualitatively from the Hamiltonian in Eq. (1); under circumstances in which there is a gap to both spin and charge excitations, the renormalization group flows carry the system to a strong coupling fixed point where the terms in $`H_{irr}`$ are no longer irrelevant, and in particular can lead to a short-range attraction between spin and charge solitons.)

Polyacetylene is a very complicated material, from a physicist’s viewpoint. It is rather disordered, even when undoped, and doping introduces all sorts of additional levels of randomness. It is moderately one-dimensional, with an in-chain bandwidth of order $`W`$10eV as compared to an interchain bandwidth of order one or two tenths of an eV; this is not, however, sufficient to permit truly one dimensional physics to be manifest at very long distances, and clearly leads to rather strong soliton confinement. Nevertheless, many rather spectacular predictions of the soliton theory, both spectroscopic and dynamical, were confirmed by experiments performed with great vigor, determination, and creativity by a large community of scientists. I think by now there can be no question that the basic features of the soliton model of polyacetylene are not only right, in theory, but applicable to a range of experiments, as well.

However, the real importance of the soliton model of polyacetylene was that it introduced a new paradigm into the field. It has led to ideas which have had a lasting impact on condensed matter physics:

* a) That there can exist quasi-particles with fractional quantum numbers (i.e. quantum numbers that are unrelated to those of an integer number of electrons and holes) that are robust entities, not just in low energy assymptopia, but in the real-world realm of materials physics;
* b) That such quasi-particles have a topological character, from which their stability derives;
* c) That these fractional quantum numbers are sharp quantum observables, every bit as real as the charge of the electron.

### A Aside: the microscopic theory of polyacetylene

Before I leave the subject of polyacetylene, there is one further point, not directly related to fractionalization, that I will touch upon. While the character of the solitons, and the separation of charge and spin are robust consequences of the broken symmetry (dimerized) groundstate, there are many aspects of the SSH solution that are more microscopic, and model dependent. In part, it was the success of some of these more delicate aspects of the theory that led to the general acceptance of the soliton model.

In particular, there was a remarkable quantitative prediction made by SSH, concerning the magnitude of the dimerization in trans polyacetylene. At the time of their first work on the subject, the in-chain bandwidth, $`W`$, was known within $`20\%`$ from various quantum chemical and band-structure calculations. Similarly, the spring constant ($`K20`$eV/$`\AA ^2`$) of the $`\sigma `$ bonds was well known to depend only on local chemistry, and so was known reliably. Thus, the only free parameter in the model was the electron-phonon coupling constant, $`\alpha `$. SSH determined the value of this parameter, empirically, by fitting to the observed optical absorption gap, and were then able to predict the magnitude of the lattice dimerization, $`u=0.04\AA `$, on the basis of this fit. Later quantitative measurements found $`u=0.03\pm 0.01\AA `$, thus confirming this prediction.

There are several things that are remarkable about this triumph of the SSH theory. The first is that this is a one dimensional system, so one might think that mean-field theory, which they employed, is unreliable. The neglect of electron-electron interactions seems, at first sight, to be equally suspect, both because these interactions are known, from quantum chemical studies of small polyenes, to be strong, and, as discussed above, interactions in the 1DEG are known to completely destroy Fermi-liquid behavior. However, this success was not an accident. The fact that the phonon frequencies, $`\mathrm{}\omega _0`$, are small on electronic scales, $`\mathrm{}\omega _0/\mathrm{\Delta }10^1`$, can easily be shown to justify the mean-field theory - indeed, effects of quantum lattice fluctuations were systematically studied and found to be quite mild. The fact that a weak-coupling theory is reasonable is guaranteed by the fact that the gap is small compared to the bandwidth, $`\mathrm{\Delta }/W10^1`$.

The proof that the effects of electron-electron interactions are largely perturbative was contained in some work I did with G.Zimanyi and A. Luther (ZKL), long after it ceased to be a hot issue. What ZKL (and, at about the same time, J.Voit, as well) did was to treat the problem of the 1DEG with both electron-electron (instantaneous) repulsions and electron-phonon induced (retarded) attractions using standard weak-coupling (one loop) renormalization group methods. What we found was that, even if at the microscopic level the electron-electron interactions are much stronger than the electron-phonon interactions, so long as $`W/\mathrm{}\omega _0`$ and $`W/\mathrm{\Delta }`$ are sufficiently large, the effective low energy theory is always dominated by the electron phonon interactions. The electron-electron interactions have the effect of renormalizing the effective electron-phonon coupling (curiously, they lead to a strong enhancement of $`\alpha `$), but other than that, have only perturbative effects on the low energy physics. Moreover, this effect is most pronounced when the electron density is commensurate, or nearly so, i.e. when there is roughly one electron per site.

Not only does this result justify, a posteriori, the remarkable physical insight of SSH, it also explains why the empirically determined value of $`\alpha `$ is large compared to those found in microscopic, quantum chemical calculations; the empirical $`\alpha `$ is a renormalized coupling. It also explains the remarkable fact that when polyacetylene is “overdoped,” i.e. when the electron concentration deviates by more than about 6% from one $`\pi `$-electron per carbon, it behaves like a nearly non-interacting metal; due to the strong doping dependence of the effective electron-phonon coupling, the expected Peierls instability of this quasi-one-dimensional metal is suppressed to immeasurably small temperatures.

## III Fractionally charged Laughlin Quasi-particles

From the first, the fact of electron fractionalization in the 1DEG and the SSH model of polyacetylene was recognized as incompatible with the conventional (Fermi liquid theory based) paradigms of condensed matter physics. However, it was widely believed at the time that this was still nothing more than a one-dimensional curiosity; there is a general theorem to the effect that solitons in a local field theory in more than one dimension have infinite creation energy, unless coupled to a suitable gauge field. Thus, it was generally expected that: 1) No “real” (i.e.  two or three dimensional) electronic system would ever exhibit true electron fractionalization. 2) The solitons of the one-dimensional theory would be confined into integer charged multiplets the moment interchain interactions were introduced. Both of these statements turn out to be wrong.

Almost immediately following the spectacular discovery of the fractional quantum Hall effect, Laughlin wrote down his famous wavefunction, which captures the essential physics of this new state of matter. An essential feature of this physics is that the quasi-particle excitations of the fractional quantum Hall liquid are vortex-like excitations with fractional charge. The fact that the fractional quantum Hall effect necessarily implies the existence of fractionally charged quasi-particles can be seen straightforwardly from a slightly modified version of the remarkable thought experiment introduced by Laughlin in his original paper:

A fractional quantum Hall liquid is an incompressible state (i.e. it has a gap, $`\mathrm{\Delta }`$) with a quantized Hall conductance

$$\sigma _H=(e^2/h)\nu ^{}$$
(2)
where $`\nu ^{}`$ is one of a set of discrete, rational fractions, of which the most prominent is $`\nu ^{}=1/3`$. Consider taking a system in its ground state which exhibits the fractional quantum Hall effect, and piercing it with an infinitesimal hole through which a magnetic flux, $`\mathrm{\Phi }`$, can be threaded. Because the system has a gap, this can be done adiabatically, so long as the rate at which the flux is threaded is slow compared to $`\mathrm{}/\mathrm{\Delta }`$. Once $`\mathrm{\Phi }`$ reaches a magnetic flux quantum, $`\mathrm{\Phi }_0=hc/e`$, the flux can be effectively removed from the Hamiltonian by a gauge transformation; the resulting state is an eigenstate of the original Hamiltonian. This new eigenstate, however, has a well defined charge which has accumulated in the vicinity of the hole. To compute the induced charge, $`Q`$, consider measuring the time integrated flux of current through a large ring which encircles the hole

$$Q=𝑑t\dot{Q}=𝑑t𝑑\stackrel{}{l}\times \stackrel{}{J}.$$
(3)
Now, the current density, $`\stackrel{}{J}`$, is the response, $`J_j=ϵ_{ij}\sigma _HE_j`$ of the quantum Hall state to the electric field $`\stackrel{}{E}(\stackrel{}{r})=c^1\dot{\stackrel{}{A}}=\widehat{r}\dot{\mathrm{\Phi }}/(2\pi r)`$ produced by the time varying flux. (Here $`ϵ_{ij}`$ is the Levi-Civita symbol.) Consequently,

$$Q=\sigma _H\mathrm{\Phi }_0=e\nu ^{}.$$
(4)
If $`\nu ^{}`$ is fractional, there must exist quasi-particles with fractional charge $`e^{}`$ such that $`ne^{}=Q`$, where $`n`$ is an integer!

The fractionally charged quasi-particles are still topological, in a sense, but in a sense which escapes the general theorem. Their topological character is manifest as fractional statistics of the Laughlin quasi-particles under exchange. This was first recognized by Halperin, from a study of the analytic properties of multi-quasi-particle wavefunctions, and later derived in a more physical manner by Arovas, Wilczek, and Schrieffer, from a calculation of the Berry’s phase when two quasi-particles are adiabatically exchanged.

As the above argument suggests, both the fractional charge and the fractional statistics of the quasi-particles are, in a sense, implicit in the fractional quantum Hall effect itself. The fractional quantization of the Hall conductance has been observed with an accuracy of better than one part in 10<sup>-4</sup>. Experiments designed to directly measure the fractional charge of the quasi-particle have been carried out, with results consistent with expectations, although with nowhere the same level of accuracy. Experiments have been proposed to directly measure the fractional statistics, as well, although they will be hard. However, there is no question in anyone’s mind that the Laughlin quasi-particles exist, that they are as robust as the fractional quantum Hall state itself, and that they have the predicted fractional charge and statistics.

One subtlety, with potentially significant consequences, is swept under the rug in the above discussion. It is possible to find circumstances in which, depending on details of the electronic Hamiltonian, there can be more than one possible quantum Hall liquid with the same value of the Hall conductance. However, these different states generally will have quasi-particles with different quantum numbers, although always consistent with the constraint that there exist multiplets with charge $`Q`$ given in Eq. 4. The macroscopic distinctions between such states can be classified in terms of the quantum numbers of the quasi-particles. Alternatively, they can be classified in terms of certain topological properties of the ground state, namely the ground-state degeneracies on closed surfaces of varying connectivities. There is, of course, an intimate connection between these two approaches. It would seem that the former is more closely related to a conceivable experiment, although the topological structure of the ground state is also related to the character of the edge states produced in a system with boundaries.

## IV RVB and spin-charge separation in two dimensions

The quantum Hall system is still very special. It is two dimensional, but so is the electron gas in real MOSFETS and heterojunction devices, among other systems. However, the large magnetic field explicitly breaks time-reversal and reflection symmetry. Thus, although following Laughlin’s work, there was no denying that fractionally charged particles were a feature of the “real” world, they still occupied a small corner of that world.

Immediately following the discovery of high temperature superconductivity, Anderson proposed that the key to the problem lay in the occurrence of a never before documented state of matter, a spin-liquid or “resonating valence bond” (RVB) state, related to a state he originally proposed for quantum antiferromagnets on a triangular (or similarly frustrating) lattice. A spin-liquid, in this context, is defined to be an insulating state (with a charge gap) and an odd integer number of electrons per unit cell which breaks neither spin-rotational nor translational symmetry. Following Anderson, Jim Sethna, Dan Rokhsar and I showed that a consequence of the existence of such a spin-liquid state is that there exist quasi-particles with reversed charge spin relations, just like the solitons in polyacetylene: charge 0 spin 1/2 “spinons” and charge e spin 0 “holons.” Indeed, these quasi-particles were recognized as having a topological character analogous to that of the Laughlin quasi-particles in the quantum Hall effect.

There was a debate at the time concerning the proper exchange statistics, with proposals presented identifying the holon as a boson, a fermion, or a semion. I now believe that all sides of this debate were correct, in the sense that there is no universal answer to the question - depending on details of the Hamiltonian, it is possible to imagine transitions occurring between states in which the holon has different statistics. In fact, this debate represented the first steps in the theoretical exploration of the topological structure of spin liquid states. We will return to this in Sec. VI B, below.

The real question-mark hanging over the whole subject, as was pointed out most forcefully by Read and Sachdev, is whether, and under what circumstances a spin-liquid exists; indeed, they presented strong arguments that the most straightforward quantum disordering of an antiferromagnet will lead to a spin-Peierls state, rather than a spin-liquid. Moreover, for more than a decade, despite extensive effort, no one succeeded in producing a model system which could be convincingly shown to exhibit a spin-liquid ground-state.

In this context, I am happy to report that very recently, Moessner and Sondhi have managed to do just this! They have considered a model on a triangular lattice (thus returning very closely to the original proposal of Anderson) which is a bit of a caricature in the sense that the constituents are not single electrons, but rather valence bonds (hard-core dimers), much in the spirit pioneered by Pauling. However, the model is sufficiently well motivated, microscopically, and the spin-liquid character sufficiently robust, that I believe it is reasonable to declare victory. Moreover, the resulting spin-liquid state does not break time-reversal symmetry. This means that the point of principle has been established. Spin charge separation (and, presumably, still more exotic forms of electron fractionalization) can occur in more than one dimension, and in the absence of either explicit or spontaneous time-reversal symmetry breaking! It is now only a matter of time until this phenomenon is either confirmed in some existing material (maybe even the high temperature superconductors), or discovered in a new system.

## V Fractionalization at quantum critical points

Electron fractionalization of a sort can occur at quantum critical points in systems between their upper and lower critical dimensions, in the sense that an injected electron will, with probability one, decay into a multi-particle continuum. However, this type of electron fractionalization is quite different from the electron fractionalization we have been discussing. In the first place, in more than one dimension, and in the limit $`T0`$, quantum critical phenomena typically occur at a critical point, as opposed to in a critical phase of matter. In the second place, there is no known quasi-particle description of the elementary excitations of such a quantum critical system; in particular, there is no currently accepted description of the critical state in terms of excitations with fractional quantum numbers.

However, there is another recent development which is exotic, but very intimately connected to the type of electron fractionalization discussed here. It was recognized a couple of years ago that a certain class of layered (i.e. quasi-two dimensional) classical systems can exhibit a critical phase, a phase, moreover, in which at low energy, the couplings between the layers are negligible. Such “floating” phases may, in fact, have been seen in lamellar DNA-lipid bilayer complexes. Moreover, a similar phenomenon can occur in the quantum theory of quasi-one dimensional systems. In such systems, even though at a microscopic level there are weak but non-vanishing couplings between chains, all interchain couplings are irrelevant in the renormalization group sense; the low energy physics of the system is that of a set of decoupled 1DEGs!

Among other things, this means that precisely the same form of one dimensional spin-charge separation discussed in the first section occurs in such systems, even though at a microscopic level there are finite higher dimensional couplings. For the models studied to date, the floating phases occur only in an extreme region of parameter space. It may be that this implies that floating phases are very rare, indeed. However, now that we know they exist in principle, we can begin looking for them. Already, there is evidence that such a floating phase occurs in one particular member of the family of high temperature superconductors.

## VI Where else might electron fractionalization occur?

I think this is the tip of the iceberg. The Fermi liquid based view of the electronic properties of solids has been very successful as a basis for understanding the essential physics of a wide range of conventional solids, including metals, semiconductors, and superconductors. It runs into difficulty in highly correlated solids, where so called “non Fermi liquid” (NFL) behavior is observed; here, even the given name admits to our complete lack of any successful theory of what causes this behavior. At best, the Landau quasi-particles are very strongly interacting in such solids. More likely, in many cases no such quasi-particle description is possible, and in some cases, electron fractionalization provides the correct framework for thinking about these systems.

### A Electron fractionalization as intermediate scale physics

While the conditions for true electron fractionalization, in the sense that it is really possible to have arbitrarily widely separated excitations with fractional quantum numbers, may be rather restrictive, the notion may be much more widely applicable.

A Fermi liquid (as contrasted with a Boltzman liquid) is only precisely defined in the limit that the temperature, $`T0`$; however, systems with a true Fermi liquid ground-state are certainly rare, at best, and may well (due to the famous Kohn-Luttinger theorem) be non-existent. Never-the-less, over a broad intermediate range of temperatures such that $`T_FTT_c`$, the Fermi liquid description is both qualitatively and quantitatively valid. (Here $`T_F`$ is the Fermi temperature and $`T_c`$ is some ordering temperature, for instance to a superconducting state.)

Similarly, there occur circumstances in which a fractionalized description of the spectrum of a system over an intermediate range of temperatures, frequencies, and length scales may be valid, even though in assymptopia it breaks down. This is certainly true of a typical quasi-one dimensional system where, at temperatures above any ordering temperature, the system can be treated as one dimensional, with the effects of interchain coupling making only perturbative corrections to the 1D physics. Even below $`T_c`$, the physics of the 1DEG is manifest at all but the lowest frequencies. Recently, considerable progress has been made in obtaining an understanding of the consequences of electron fractionalization for various electronic spectroscopies of correlated electronic systems, and on the nature of the crossover from a fractionalized spectrum above $`T_c`$ to a spectrum with a well defined quasi-particle piece below $`T_c`$. In many respects, these spectra account well for properties of the observed spectra (especially those obtained in angle resolved photoemission) in the high temperature superconductors, including many features that simply cannot be understood in the context of Fermi liquid theory. It has also been suggested, that spin-charge separation at intermediate scales may generally be the basis of an electronic mechanism of high temperature superconductivity.

### B Topological order and electron fractionalization

We now address the problem of classifying phases in which true electron fractionalization occurs, e.g. in which spinons are deconfined. It is now clear from the work of Wen and Senthil and Fisher that the best macroscopic characterization of fractionalized phases in two or more dimensions, given that they frequently posses no local order parameter, is topological. Specifically, a fractionized phase exhibits certain predictable ground-state degeneracies on various closed surfaces - degeneracies which Senthil and Fisher have given a physical interpretation in terms of “vison expulsion.” Unlike the degeneracies associated with conventional broken symmetries, these degeneracies are not lifted by small external fields which break either translational or spin rotational symmetry. It has even been shown (funny as this may sound) that topological order is amenable to experimental detection. Once topological classification is accepted, the one-to-one relation between spin-liquids and electron fractionalization, implied in our previous discussion, is eliminated. Indeed, it is possible to imagine ordered (broken symmetry) states, proximate to a spin liquid phase, which will preserve the ground-state degeneracies of the nearby spin liquid, and hence will exhibit spin-charge separation.

### C Electron fractionalization and quantum computing

One of the most exciting areas where electron fractionalization may play an important role is in the developing field of quantum computing. It was recently shown that many of the vexing problems of decoherence, which are barriers to construction of a functioning quantum computer, can be avoided if the quantum states in question have an appropriate topological character. Certain types of electron fractionalization, including those which occur in some complicated quantum Hall states and in the RVB spin-liquid, have topological structure that could be useful for this purpose. Here, even if (as seems likely) rather special circumstances are required to obtain true electron fractionalization, it may be worthwhile to seek artificial methods for achieving those special circumstances.

Acknowledgements: Substantial improvements in this manuscript were made in response to comments by M.P.A.Fisher, E.Fradkin, C.Nayak and S.Sachdev.