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# Adsorption of charged particles on an oppositely charged surface: Oscillating inversion of charge

## I Introduction

Adsorption of charged particles on the surface of an oppositely charged macroion is an important problem with broad applications in many areas of science. In a water solution, double helix DNA, actin, charged colloids, charged membranes or any charged interfaces can play the role of the macroion. Charged particles, or counterions, in solution can be ions, small colloids, charged micelles, short or long polyelectrolytes. Mean field theories based on the Poisson-Boltzmann equation and its linearized version, the Debye-Hückel equation, have been used to study such screening problem. There are, however, several new phenomena in solutions containing multivalent counterions which cannot be explained using standard mean-field theories. The most notorious of all is probably the charge inversion, a counter intuitive phenomenon in which a macroion strongly binds so many counterions that its net charge changes sign. This can be thought of, theoretically, as overscreening. It cannot be explained using Poisson-Boltzmann theory because, in a mean field theory, screening compensates at any finite distance only a part of the macroion charge. Charge inversion recently has attracted significant attention.

It was shown that charge inversion is driven by the counterion correlations which are ignored in mean field theories. When multivalent counterions condense on the surface of a macroion to screen its charge, due to their strong lateral repulsion they form a two-dimensional strongly correlated liquid. To see when correlation is important in this liquid, one first defines a dimensionless parameter $`\mathrm{\Gamma }`$ which measures the strength of the interaction energy between counterions in units of the thermal energy: $`\mathrm{\Gamma }=(Ze)^2(\pi n)^{1/2}/Dk_BT`$, where $`D80`$ is the dielectric constant of water, $`Ze`$ is the charge of a counterion (for convenience, we call it a $`Z`$-ion) and $`n`$ is the two-dimensional concentration of $`Z`$-ions condensed on the macroion surface. Without loss of generality, we assume through out this paper that $`Ze`$ is positive and the macroion is negatively charged with the surface charge density $`\sigma `$. For a strongly charged macroion with surface charge density $`\sigma 1e/nm^2`$, $`\mathrm{\Gamma }1.2,3.5,6.4`$ and $`9.9`$ at $`Z=1,2,3`$ and $`4`$. Thus, for $`Z3`$, $`\mathrm{\Gamma }`$ is a large parameter of the theory and the two-dimensional system of $`Z`$-ions is a strongly correlated liquid (SCL). It has short range order very similar to a two-dimensional Wigner crystal (See Fig. (1)). At the same time, large parameter $`\mathrm{\Gamma }`$ also guarantees the layer of $`Z`$-ions at the macroion surface is effectively two-dimensional. Indeed, each $`Z`$-ion, in the uniform field $`2\pi \sigma `$ of the macroion surface, moves within a distance $`Dk_BT/2\pi \sigma Ze0.52A/\mathrm{\Gamma }`$ from the macroion surface. At large $`\mathrm{\Gamma }`$, this distance is much smaller than average distance $`2A`$ between $`Z`$-ions in the direction parallel to the macroion surface. This makes the $`Z`$-ion layer effectively two-dimensional.

The correlation physics explains charge inversion as follows. When a new $`Z`$-ion comes to the macroion which is already neutralized by the $`Z`$-ion layer, it pushes other ions aside and creates a negative background charge for itself. In other words, it creates an oppositely charged image (or a correlation hole) in the $`Z`$-ion layer (Fig. 2a). Due to the attraction from this image, the $`Z`$-ion sticks to the surface and overcharges it. The overcharging saturates when the positive inverted net charge of the macroion is large enough to counterbalance the above mentioned attractive force. In a more quantitative language, correlation induced attraction to the $`Z`$-ion layer can be explained as a result of the negative chemical potential $`\mu _{SCL}`$ of SCL, whose magnitude is much larger than $`k_BT`$ ($`|\mu _{SCL}|\mathrm{\Gamma }k_BTk_BT`$).

In this paper, we would like to investigate the problem of charge inversion further by considering the effect of the excluded volumes of $`Z`$-ions. This effect was studied in Poisson-Boltzmann approach. Here we show that in the correlation theory, this effect can lead to qualitatively new consequences. When the charge of the macroion increases, $`A`$ decreases and $`\mathrm{\Gamma }`$ increases, the correlation between $`Z`$-ions becomes stronger. In other words, $`|\mu _{SCL}|`$ increases and charge inversion is stronger. However, the excluded volume has a dramatic consequence when $`Aa`$: the pressure of the SCL liquid diverges and it becomes effectively incompressible.

In this case, the correlation image and charge inversion disappears (Fig. 2b). If the macroion charge increases further, however, a second layer of $`Z`$-ions is created and charge inversion recovers (Fig. 2c). Here everything is repeated again but with the role of $`\sigma `$ played by the net charge of the macroion and the first full layer. Consequently, if one plots the net charge of the macroion versus its bare charge, one sees an oscillation of charge inversion: every time a new layer of $`Z`$-ions forms on the macroion surface, charge inversion appears and steadily increases with increasing macroion charge then drops quite abruptly when the layer starts to become full (see Fig. 3). As a result of these oscillations, the maximum value of the inverted net charge is limited, no matter how large the charge of the macroion is. To our knowledge, this is the first time this periodical behaviour is suggested.

This paper is organized as follows. In Sec. II, we derive an analytical formula for the chemical potential of the $`Z`$-ions condensed on the macroion surface taking into account the excluded volume effect. This chemical potential is then used to calculate the inverted charge of the macroion. In Sec. III, a Monte Carlo simulation of a small system is used to verify the analytical predictions of Sec. II. In Sec. IV, we consider the role of charge inversion in the case of screening of a metallic electrode, whose potential is tuned instead of surface charge density $`\sigma `$. We show that, in this case, correlations lead to the oscillations of the macroion capacitance.

## II Chemical potential of $`Z`$-ions with hard-core repulsion.

To understand the electrostatics of the system, let us start with a two-dimensional system of point charges ($`a=0`$) with concentration $`n`$ on a neutralizing background charge. Conventionally, this system is referred to as a one component plasma. Excluded volume effects will be considered later. At large parameter $`\mathrm{\Gamma }`$, the plasma is a strongly correlated liquid (SCL) whose short range order is very similar to a Wigner crystal (WC). Specifically, the energy per $`Z`$-ion $`\epsilon _{SCL}(n)`$ of a SCL can be very well approximated by that of a WC, which in turn can be approximated by the energy of a Wigner-Seitz cell because quadrupole-quadrupole interactions between neutral Wigner-Seitz cells are very small. This gives

$$\epsilon _{SCL}(n)\epsilon _{WC}(n)1.10\frac{Z^2e^2}{AD}.$$
(1)
A more accurate calculation gives $`\epsilon _{WC}(n)`$ a slightly higher value:

$$\epsilon _{WC}(n)1.06Z^2e^2/AD.$$
(2)
Knowing $`\epsilon _{WC}(n)`$, the chemical potential of the WC can be easily calculated:

$$\mu _{WC}(n)=\frac{[n\epsilon _{WC}(n)]}{n}1.57\frac{Z^2e^2}{AD}=1.65\mathrm{\Gamma }k_BT$$
(3)
Thus, $`\mu _{WC}(n)`$ is negative and much larger than $`k_BT`$. It acts as an additional attraction to the macroion surface which in turn leads to the charge inversion effect. The temperature correction to $`\mu _{WC}(n)`$, or in other words, the difference between $`\mu _{SCL}(n)`$ and $`\mu _{WC}(n)`$, has been calculated numerically  for a wide range of the parameter $`\mathrm{\Gamma }`$ and indeed is very small and can be neglected. For example, it is equal to 11% at $`\mathrm{\Gamma }=5`$ and 5% at $`\mathrm{\Gamma }=15`$.

Now let us return to our problem of finite size $`Z`$-ions. As the detail derivation in the appendix shows, the chemical potential of a $`Z`$-ion with hard-core repulsion can be written as the sum

$$\mu (n)=\mu _0(n)+\mu _{WC}(n),$$
(4)
where $`\mu _0`$ is the chemical potential of a system of neutral hard discs of radius $`a`$ at the same concentration $`n`$. In writing down Eq. (4), the electrostatic contribution to $`\mu (n)`$ has been approximated by $`\mu _{WC}(n)`$, in exactly the same way $`\mu _{SCL}(n)`$ was approximated by $`\mu _{WC}(n)`$ above. The temperature correction to $`\mu _{WC}(n)`$, in this case, is even smaller than that for the SCL of point charges because due to the hard-core repulsion, two $`Z`$-ions are never at a distance less than $`2a`$ from each other. Furthermore, this correction decreases when $`A`$ decreases making the approximation by $`\mu _{WC}(n)`$ increasingly better and asymptotically exact when $`Aa`$.

To proceed further, one needs to calculate the chemical potential $`\mu _0(n)`$. The hard disc and hard sphere systems have been extensively studied both analytically and numerically providing significant insights into solid-liquid phase transition and the melting process (See Ref.  and references therein). In this paper, to emphasize the effects of excluded volume, we would like to repeat here simple calculations using the free volume approximation which is asymptotically exact near the close packing limit.

To calculate $`\mu _0`$, one notices that because of the hard-core repulsion, the area $`s`$ available per each disc is smaller than the area $`2\sqrt{3}A^2`$ of a Wigner-Seitz cell (See Fig. 4).

A simple calculation shows that near the close packing limit, $`s=\alpha (Aa)^22\sqrt{3}A^2`$, where $`\alpha 4.62`$. To calculate the free energy of the quasi two-dimensional layer of $`Z`$-ions, one needs to add a third out-of-surface dimension. The typical distance $`x`$ of the out-of-surface motion of a $`Z`$-ion is the distance at which the energy cost for moving the $`Z`$-ion away from the plane is of the order of $`k_BT`$. Solving $`2\pi \sigma Zex/Dk_BT`$ gives $`x=Dk_BT/2\pi \sigma Ze=\mathrm{\Lambda }`$ which coincides with the Gouy-Chapman distance (note that this estimation of $`x`$ is consistent because, for $`\mathrm{\Gamma }1`$, $`\mathrm{\Lambda }A`$, all other $`Z`$-ions are far apart and we can use the planar electric field $`2\pi \sigma /D`$ for the calculation of $`x`$.) Now, one can estimate the free energy of the hard disc system as the free energy of an ideal gas with concentration $`1/s\mathrm{\Lambda }`$:

$$F_0=Nk_BT\left(\mathrm{ln}\frac{s\mathrm{\Lambda }}{v_0}+1\right),$$
(5)
where $`N`$ is the number of adsorbed $`Z`$-ions and $`v_0`$ is the normalizing volume which can be thought of as the volume of one water molecule. The exact value of $`v_0`$ is not important because it drops out of all final results.

The chemical potential of adsorbed $`Z`$-ions is, correspondingly:

$`\mu _0={\displaystyle \frac{F_0}{N}}`$ $`=`$ $`k_BT\left(\mathrm{ln}{\displaystyle \frac{v_0}{s\mathrm{\Lambda }}}1\right)k_BT{\displaystyle \frac{N}{s}}{\displaystyle \frac{s}{N}}`$ (6)
$``$ $`k_BT\left(\mathrm{ln}{\displaystyle \frac{v_0}{\alpha (Aa)^2\mathrm{\Lambda }}}1\right)+k_BT{\displaystyle \frac{A}{Aa}}.`$ (7)
From Eq. (7), one can see that when $`Aaa`$, this chemical potential is positive and very large what negates any gain from the electrostatic part $`\mu _{WC}`$. Charge inversion therefore disappears in this limit and will not recover until the second layer builds up when the macroion charge grows.

Using the correlation hole concept mentioned in the introduction, one can easily understand why charge inversion disappears. The second term in Eq. (7), which is the dominant term when $`A`$ approaches $`a`$, is nothing but $`p_0/n`$, where $`p_0=F_0/S=nk_BTA/(Aa)`$ is the two-dimensional pressure of the hard disc system near the close packing limit, $`S`$ is the total area of the macroion surface. The divergence of the pressure leads to the zero compressibility of the $`Z`$-ion layer when $`Aa`$. When a new $`Z`$-ion approaches this layer, it cannot put other $`Z`$-ions aside to create its correlation hole to attract to it (Fig. 2b). Therefore, charge inversion disappears.

It should be noted that, even though Eq. (5) is expected to be asymptotically correct only near the close packing limit ($`Aa`$), where the hard disc system is known to be in the solid phase, it is actually quite good as an approximation in the whole range of $`A`$. Indeed, Monte-Carlo simulations and molecular dynamics calculations (See Ref. ) show that the pressure obtained using the free volume approximation gives an excellent result for the solid phase of the hard disc system and a good result for the liquid phase. The biggest discrepancy occurs around the liquid-solid phase transition is only about 20%. Combining with the fact that, for large $`\mathrm{\Gamma }`$, the electrostatic contribution $`\mu _{WC}`$ is the dominant term of $`\mu `$ everywhere except near close packing, we can reliably use Eq. (4) for the $`Z`$-ion chemical potential.

Let us now calculate the net charge of the macroion which is the total charge of the macroion and the $`Z`$-ion layer on its surface. To do so, one has to balance the electro-chemical potential of the $`Z`$-ions at the macroion surface with the electro-chemical potential $`\mu _b`$ of $`Z`$-ions in the bulk solution. If we assume the concentration of the $`Z`$-ions in the bulk solution is $`c`$, this balance in electro-chemical potential reads:

$$\mu +Ze\psi (0)=\mu _bk_BT\mathrm{ln}(cv_0),$$
(8)
where $`\psi (0)=2\pi \sigma ^{}r_s`$ is the averaged macroscopic electrostatic potential at the macroion surface due to the net charge density $`\sigma ^{}=\sigma +Ze/2\sqrt{3}A^2`$ of the macroion surface with $`Z`$-ions condensed on it, $`r_s`$ is the screening length of the solution. On the right side of Eq. (8), the bulk solution (where the electrostatic potential vanishes) is assumed to be ideal so that $`\mu _b`$ is approximated by the ideal gas chemical potential $`k_BT\mathrm{ln}(cv_0)`$.

Substituting Eq. (4) and (7) into Eq. (8), one gets:

$$Ze\psi (0)=|\mu _{WC}|k_BT\mathrm{ln}\frac{1}{\alpha (Aa)^2\mathrm{\Lambda }c}k_BT\frac{a}{Aa}.$$
(9)
Because $`\mu _{WC}`$ is negative and much larger than $`k_BT`$ in absolute value, one can see from Eq. (9) that, if $`A`$ is not very close to $`a`$, the last two terms on the right hand side can be neglected. In this case, $`\psi (0)`$ and therefore $`\sigma ^{}`$ are positive. Recalling that the bare charge density $`\sigma `$ of the macroion is negative, we see a charge inversion effect: the amount of $`Z`$-ions adsorbed by the macroion surface is larger than needed to neutralize its charge. Eq. (9) clearly shows that this effect is driven by correlations since the correlation part $`|\mu _{WC}|`$ of the chemical potential is the only positive term in the right hand side.

It is interesting to mention the limiting case of Eq. (9) in which $`Z`$-ions are point charges ($`a=0`$). At high enough bulk concentration $`c`$ or low enough temperature $`T`$, Equation (9) then gives $`Ze\psi (0)=|\mu _{WC}|`$. For a spherical macroion, its surface potential is $`\psi (0)=Q^{}/r_MD`$ ($`r_M`$ is the macroion radius, $`Q^{}`$ is the macroion net charge). This gives:

$$Q^{}=0.84\sqrt{QZe},$$
(10)
where $`Q`$ is the macroion bare charge. This is the maximum possible inverted charge of a spherical ion. Surprisingly, this charge does not depend on the macroion radius. This function $`Q^{}(Q)`$ is plotted in Fig. 3 by the dashed line.

For $`Z`$-ions with finite radius $`a`$, when $`A`$ approaches $`a`$ the last two terms in Eq. (9) increase substantially and reduce charge inversion. When a near complete layer of $`Z`$-ion is formed ($`Aaa`$), these terms eventually become bigger than $`|\mu _{WC}|`$. When this happens, $`\sigma ^{}`$ becomes negative and charge inversion disappears. If one increases the macroion charge further, the second layer of $`Z`$-ions appears on the surface of the macroion and the charge inversion recovers. Now, one can still use Eq. (9) to calculate charge inversion provided the bare charge of the macroion is replaced by the net charge of the macroion with the first layer of $`Z`$-ion $`\sigma _1=\sigma +Ze/2\sqrt{3}a^2`$. Similarly, as the macroion ion charge increases further one obtains a periodic behaviour of charge inversion with respect to the increase of macroion charge: charge inversion disappears every time a layer of $`Z`$-ions is near full and recovers when new layer appears. This oscillating behaviour is shown in Fig. 3 where the solution to Eq. (9) is plotted. In Fig. 3, there are small regions near the beginning of each layer where the net charge density of the macroion with full layers is so small that $`\mathrm{\Gamma }<1`$. In such a region, Eq. (9) cannot be used to describe screening of the macroion surface. Instead, when $`\mathrm{\Gamma }<1`$, correlations can be neglected and one should use the standard Poisson-Boltzmann mean-field screening theory. Hence, in this region the net charge is the same as the bare macroion charge ($`\sigma ^{}<0)`$. As $`\sigma `$ increases, however, $`\mathrm{\Gamma }`$ soon reaches unity and charge inversion takes over.

It should also be noted here that, in all above calculations, the dielectric constant of the macroion was implicitly assumed to be equal to the dielectric constant $`D`$ of water solution so that all $`Z`$-ions lie on the macroion surface. In general, the dielectric constant of a macroion is smaller than water so that a $`Z`$-ion approaching the surface sees an additional repulsive force from its electrostatic image in the macroion due to the discontinuity in the dielectric constant at the macroion-water interface. This additional image pushes the $`Z`$-ion off at a distance from the surface and reduces the attractive force created by the correlation hole in the adsorbed $`Z`$-ion layer calculated above. However, all the oscillating charge inversion picture mentioned above remains valid qualitatively. Indeed, it is shown in Ref.  that the additional image charge lifts each $`Z`$-ion off the surface by a distance of the order of $`A/4`$ and reduces the correlation energy approximately by half, thus $`\mu _{WC}`$ remains highly negative and charge inversion is preserved.

## III Monte-Carlo simulation

To demonstrate the oscillating behaviour of charge inversion, we carry out Monte-Carlo simulations of a small system of a macroion with $`Z`$-ions. The $`Z`$-ions are modeled as charged spheres with charge $`Z=4`$ and radius $`a=0.9l_B`$, where the Bjerrum length $`l_B=e^2/Dk_BT`$. The system is simulated at room temperature ($`298^{}`$K) so that $`l_B7.2`$Å. The macroion has radius $`r_M=3.5l_B`$. Thus, a full (hexagonal close-packing) first layer of $`Z`$-ions would contain $`4\pi r_M^2/2\sqrt{3}a^286`$ $`Z`$-ions if one does not take into account defects caused by the finite curvature of the macroion surface (one cannot put a perfect crystal on the surface of a sphere). The actual number of $`Z`$-ion at full filling should be smaller. In our Monte-Carlo simulation, in part also due to the divergence of pressure mentioned in the previous section, the number of $`Z`$-ions in the first layer never exceeds 75.

The macroion charge $`Q`$ is varied from 20 to 550 so that at maximum there are two layers of $`Z`$-ions on the macroion surface. Energies of interaction between two $`Z`$-ions and between each $`Z`$-ion and the macroion were calculated according to unscreened Coulomb law $`(Ze)^2/Dr_{ij}`$ and $`ZQe^2/Dr_{Mi}`$, where $`r_{ij}`$ is the distances between centers of the two $`Z`$-ions numbered $`i`$ and $`j`$, and $`r_{Mi}`$ is the distances between the centers of the $`Z`$-ion numbered $`i`$ and the macroion. The net macroion charge $`Q^{}=Q+NZe`$ is determined from the result of the simulation where $`N`$ is the number of $`Z`$-ions adsorbed on the macroion. A $`Z`$-ion is considered adsorbed if its center is found within a distance $`3a`$ from the top full layer of the $`Z`$-ion (or from the macroion surface if there’s only one partially filled layer). The whole system is positioned inside a hard spherical shell with large radius $`L=17.4l_B`$ with the macroion fixed at the center of the shell (see Fig. 5).

In our simulated system, the total charge of the macroion and all the $`Z`$-ions is $`220e`$, so that the total charge of $`Z`$-ions is larger than the macroion charge. This is needed to observe charge inversion. In practical situation, the excess charge of $`Z`$-ions is neutralized by monovalent ions at the distance of the order of the screening length $`r_s`$ from the macroion surface. In our simulation, these excess $`Z`$-ions are neutralized at the external hard spherical shell instead (it would be too time consuming to simulate the monovalent ions). This difference, however, produces no significant impact on the charge inversion because of the short range nature of correlations. Indeed, it is shown in Ref.  that if $`r_s`$ is larger than radius of the macroion, charge inversion only weakly depends on $`r_s`$. This is because the capacitance of the macroion screened at the distance much larger than its radius only weakly depends on $`r_s`$. In the same way, charge inversion of the macroion in the shell is almost independent on the shell radius when it is much larger then macroion radius. This is because the capacitance of macroion-shell capacitor is almost constant, while it is charged by the negative chemical potential of $`Z`$-ion which is determined by interactions at the distances of the order of the size correlation hole, $`A`$, from the macroion surface.

For most of the Monte-Carlo attempted moves, the new position of a randomly chosen $`Z`$-ion is chosen with uniform distribution in a cube with size $`l_B`$ centered at the old $`Z`$-ion position. However, once in every 100 attempts, a longer attempted move is made: If the chosen $`Z`$-ion is found in the vicinity of the macroion ($`r_M<r<r_M+2a`$, where $`r`$ is the distance from the $`Z`$-ion to the macroion center), it is attempted to move to the vicinity of the external shell ($`L3.5a<r<L`$). Vice versa, if the chosen $`Z`$-ion is found in the vicinity of the external shell, it is attempted to move to the vicinity of the macroion. This is done to quickly equilibrate the system and to overcome the huge Coulomb barrier which results from the combination of short range attraction of a $`Z`$-ion to its image in the SCL and the repulsion from the inverted macroion charge. The usual Metropolis algorithm is used to reject or accept a move. Typically, in a simulation run, the number of attempted moves per $`Z`$-ion is $`2\times 10^6`$, of which the last $`1\times 10^6`$ moves are used for averaging of $`Q^{}`$.

A snapshot of the complex of the macroion and the $`Z`$-ions condensed on it is shown in Fig. 6 for the case the macroion charge is $`220e`$. The net macroion charge in this case is $`12e`$ (the macroion is overscreened).

The simulation results are shown in Fig. 7, where the macroion net charge $`Q^{}`$ is plotted against the macroion bare charge $`Q`$ together with our theoretical prediction. As we expected, the charge inversion disappears ($`Q^{}`$ goes to zero) near complete filling. After that, the second layer of condensed $`Z`$-ions starts to form and the macroion is undercharged initially. When $`Q`$ increases further so that more $`Z`$-ions come to the second layer and correlations become important, charge inversion soon recovers and increases with $`Q`$.

In order to compare our theory with simulation results some modifications are necessary. Because of the presence of the hard shell which confines the $`Z`$-ions, Eq. (8) should read:

$$\mu +Ze\psi (0)=k_BT\mathrm{ln}(c_Lv_0)+Ze\psi (L),$$
(11)
where in the right hand side, the bulk concentration $`c`$ is replaced by the concentration $`c_L`$ at distance $`L`$. Because $`c_L`$ is small, we still assume ideal solution neglecting $`Z`$-ion correlations (so that the chemical potential of $`Z`$-ions at distance $`L`$ is $`k_BT\mathrm{ln}(c_Lv_0)`$). The potential $`\psi (L)=ZeQ^{}/DL`$ obviously does not vanish at distance $`L`$.

Correspondingly, Eq. (9) is replaced by:

$`Ze[\psi (0)\psi (L)]`$ $`=`$ $`|\mu _{WC}|k_BT\mathrm{ln}{\displaystyle \frac{1}{\alpha (Aa)^2\mathrm{\Lambda }c_L}}`$ (13)
$`k_BT{\displaystyle \frac{a}{Aa}}.`$
In the simulation, the $`Z`$-ion concentration $`c_L`$ (hence, their chemical potential) is kept relatively constant by choosing the number of $`Z`$-ions at any $`Q`$ in such a way that after neutralizing the macroion charge, there are 55 $`Z`$-ions left. As one can see from Fig. 7, the oscillations of the number of $`Z`$-ions adsorbed at the macroion surface do not exceed 4. Such a small deviation in the number of free $`Z`$-ions from 55 only weakly affects $`c_L`$. Furthermore, due to the excess charge of these extra $`Z`$-ions, they spread out in a thin layer near the outer boundary where their charges are neutralized. This helps to keep $`c_L`$ relatively constant. Because in Eq. (13), $`c_L`$ appears under the logarithmic function, the chemical potential of $`Z`$-ions oscillates even weaker than $`c_L`$.

The solution to Eq. (13) is plotted by the solid line in Fig. 7. As we can see, although the theoretical prediction agrees favourable with the Monte Carlo results, it overestimates the net inverted charge near the full filling. This discrepancy is due to the use of a planar hard disc system in the theory of the $`Z`$-ion layer at the macroion surface. Indeed, unavoidable lattice defects caused by the curvature of the macroion surface (there are 12 disclinations and a number of dislocations in the $`Z`$-ion layer) can lead to a large misprediction of the number of $`Z`$-ions at complete filling if we assume a flat layer with the same area. For example, calculations using icosahedron show that even in the optimal situations with “magic” numbers of $`Z`$-ions, planar geometry mispredicts the number of $`Z`$-ion at complete filling by 1 for $`N=12`$ and by 3 for $`N=32`$. Away from the magic numbers where a number of dislocations appear, this misprediction is even larger. The dash line in Fig. 7 is the adjusted theoretical prediction of Eq. (13) assuming the number of $`Z`$-ions at maximum filling of the first layer is 79 instead 86. The agreement between this curve and the Monte Carlo results is much better than the solid curve. It should be noted that, defects are important only near complete filling where the $`Z`$-ions layer forms a real solid. At smaller filling where $`Z`$-ion layer is liquid like, defects play no role. That is why the adjusted prediction (the dash line in Fig. 7) is not drawn at smaller filling. Obviously, at larger macroion size, the region where defects are important is relatively smaller.

The planar approximation of the macroion surface also forces us not to extend theoretical prediction to $`Q<48`$ (or 12 $`Z`$-ions) because, at small $`Q`$, the average distance between $`Z`$-ions on the macroion surface $`2A=\sqrt{8\pi (r_M+a)^2Ze/\sqrt{3}Q}`$ is larger than the radius $`r_M`$ of the macroion. This makes the concept of a two-dimensional $`Z`$-ion layer, and therefore Eq. (13), quantitatively incorrect. Again, if the macroion size gets larger or the $`Z`$-ion size gets smaller, the $`Z`$-ion layer can be truthfully regarded as two-dimensional in a larger region of $`Q`$. This in turn makes Eq. (13) applicable quantitatively in a wider region of $`Q`$. It should be noted that, even though Eq. (13) fails at small $`Q`$ in our case, the qualitative picture of charge inversion is still valid. This is because, in our case, the plasma parameter $`\mathrm{\Gamma }`$ is still large and does not reach unity until $`Q2`$.

## IV Voltage controlled oscillations of charge and capacitance

In the previous sections, we discussed the oscillating behaviour of the inverted charge as a function of the macroion charge. Generally speaking tuning the charge of an insulating macroion is not a trivial task, although can be done . We propose here an alternative experiment that would show this oscillating behaviour when the macroion surface potential is tuned instead. It is sketched in Fig. 8.

The role of the macroion is played by the left metallic plate covered by an insulator layer with thickness $`d`$, surface area $`S`$ and dielectric constant $`D_i`$. The other side of the dielectric is in contact with the ionic solution which contains the $`Z`$-ions. Some of $`Z`$-ions condense on the dielectric surface to screen the electric field created by the negative charges on the metal plate. By changing the voltage $`V`$ applied to the other plate, one can easily vary the charge of condensed $`Z`$-ions on the dielectric surface. We show below that if one measures the differential capacitance of this systems as a function of $`V`$, one can expect an oscillating behaviour.

To deal with a macroion at a constant potential, our theory needs some modifications. When the voltage $`V`$ is applied, a charge $`Q`$ is induced on the left metallic plate. $`Z`$-ions layer with total charge $`Q_t`$ is then formed on the dielectric surface in solution to screen the electric field of the plate. The excess charge $`Q^{}=Q_tQ`$ due to overscreening is in turn linearly screened at the distance $`r_s`$ in the solution. Due to the electro-neutrality of the solution, charge $`Q`$ appears on the other side of the solution container to screen the second metallic plate. If $`d`$ is large enough ($`dA`$) so that one can neglect the image of $`Z`$-ions in the left metallic plate, the free energy of the system can be written as:

$$F=\frac{Q^2}{2C(d)}+\frac{Q^{\mathrm{\hspace{0.17em}2}}}{2C(r_s)}+N\epsilon (n)+\frac{Q^2}{2C(r_s)}QVN\mu _b,$$
(14)
where $`Q`$ is the charge, $`C(d)=D_iS/4\pi d`$ is the capacitance and $`Q^2/2C(d)`$ is the energy of the planar capacitor formed by the dielectric layer with thickness $`d`$. As we mentioned above, the excess charge $`Q^{}`$ is linearly screened at distance $`r_s`$ in solution. The free energy of this screening atmosphere can be expressed as the energy of a capacitor with charge $`Q^{}`$, thickness $`r_s`$ and capacitance $`C(r_s)=DS/4\pi r_s`$ (The second term in Eq. (14)). The third term in Eq. (14) accounts for the correlation energy of the SCL of $`Z`$-ions condensed at the dielectric surface ($`N=Q_t/Ze`$ is the number of $`Z`$-ions condensed and $`n=N/S`$ is their two-dimensional concentration). The fourth term in Eq. (14) is the energy of the capacitor with thickness $`r_s`$ on the right side of the solution container. On this side only monovalent ions screen the electrode. Therefore correlations are weak and screening can be described by the usual linear theory which gives the free energy $`Q^2/2C(r_s)`$. The fifth term in Eq. (14), $`QV`$, is the work the source does to maintain the system at the constant voltage $`V`$. Finally, the last term in Eq. (14) is the change in the free energy of the bulk solution which acts as a reservoir to provide the $`Z`$-ions to the macroion surface.

Minimizing the free energy (14) with respect to the unknown parameters $`Q`$ and $`Q_t`$, one gets:

$`V=Q\left(C(d)^1+2C(r_s)^1\right)Q_tC(r_s)^1,`$ (15)
$`(\mu (n)\mu _b)/Ze=Q^{}C(r_s)^1.`$ (16)
As shown in previous sections, due to correlations between $`Z`$-ions, $`(\mu (n)\mu _b)`$ is positive everywhere except near complete filling. According to Eq. (16), this means that $`Q^{}`$ is positive, indicating charge inversion.

Solving Eqs. (15) and (16), one gets

$$V=Q\left(C(d)^1+C(r_s)^1\right)+\frac{\mu (n)\mu _b}{Ze},$$
(17)
which shows that the correlation between $`Z`$-ions condensed on the dielectric surface works as an additional voltage applied to the system.

A measurable quantity of the system is its differential capacitance $`C=Q/V`$, or

$$C^1=\frac{V}{Q}=C(d)^1+C(r_s)^1+\frac{1}{Ze}\frac{\mu (n)}{n}.$$
(18)
As we saw in previous sections, excluded volume effect leads to the oscillations in the chemical potential $`\mu (n)`$ of the $`Z`$-ions which becomes positive every time a full layer of $`Z`$-ions is developed. From Eq. (18), this ultimately results in the oscillations of the inverse capacitance $`C^1`$ of the system. Thus measuring $`C(V)`$ one can indirectly observe the oscillations in charge inversion.

Concluding this section, we would like to mention that the oscillations of the differential capacitance we obtained above are remarkably similar to the well known oscillations in the compressibility and magneto-capacitance in the two-dimensional electron gas in quantum Hall regime . In this case, the oscillations are related to the consecutive filling of Landau levels. The compressibility of the two-dimensional electron gas vanishes every time a Landau level is fully occupied. In our system, the two-dimensional electron gas is replaced by the quasi two-dimensional liquid of $`Z`$-ions and the magnetic field is replaced by the varying voltage. In this sense, we can say that we are dealing with a classical analog of the quantum Hall effect.

## V Conclusion

Summarizing our results, we have shown that the excluded volume of $`Z`$-ions can dramatically change the screening of a macroion by $`Z`$-ions. In particular, charge inversion is shown to oscillate with the macroion surface charge density $`\sigma `$. At small macroion surface charge density, it increases with $`\sigma `$. However, when the surface charge is high enough so that a near full layer of $`Z`$-ion is formed, charge inversion disappears quickly because of the vanishing compressibility of a full layer of $`Z`$-ions. Charge inversion recovers when $`\sigma `$ increases further so that a second layer of $`Z`$-ions builds up. Since tuning of the charge of an insulating macroion is not a simple task, we also propose an experimental setup with metallic electrodes playing the role of a macroion. This experiment can be used to indirectly observe these oscillations of charge inversion.

Oscillations of charge inversion discussed in this paper are related to the hard-core repulsion of spherical $`Z`$-ions. Similar effect should exist for the adsorption of rigid rod-like polyelectrolytes (PE) on oppositely charged surface. On a strongly charged surface rods can form more than one layer leading to a deep minimum of the charge inversion every time when the top layer is completely full. It is important that charge inversion in both cases is determined by the top layer.

It is interesting to discuss the relation between our work and the recent theory of adsorption of a thick layer of weakly charged, flexible PE with excluded volume  in which no oscillations of charge inversion with the increasing surface charge density of macroion, $`\sigma `$, was found. Instead, the inverted charge reaches a constant maximum value when PE molecules start to overlap. The picture described in Ref.  is as follows. A flexible PE molecule in solution can be viewed as a rod-like string of Gaussian electrostatic blobs. Each such blob has a quite low density of polymer. At small absolute value of $`\sigma `$, PE rods screen the macroion surface forming correlated liquid of locally parallel rods which overcharges the macroion. As $`\sigma `$ increases, charge inversion also increases until, at some value of $`\sigma `$ which the authors call $`\sigma _e`$, the blobs start overlapping with each other. In contrast with the hard-core repulsion case, blobs are easily compressible. Therefore, when the surface charge $`\sigma `$ increases further, the adsorbed PE molecules form a scaling structure of layers of blobs with increasing size and decreasing density from the bottom to the top. In the top layer, blobs have the same size as unperturbed blobs in the solution. As in the case of hard core compact $`Z`$-ions, it is this top layer which is responsible for the image of an approaching new PE molecule and, therefore, for the correlation induced charge inversion. According to Ref. , in the case of flexible weakly charged PE the properties of the top layer do not oscillate with $`\sigma `$ because newly adsorbed PE molecules lead to an additional compression of lower layers. Thus at $`\sigma >\sigma _e`$, the inverted charge does not oscillate and remains the same as at $`\sigma =\sigma _e`$.

###### Acknowledgements.

We are grateful to A. Yu. Grosberg, V. Lobaskin, W. Halley and M. Rubinstein for useful discussions. This work was supported by NSF DMR-9985785.

## VI appendix

To derive the chemical potential (4), let us start with the standard relationship between the free energy and the canonical partition function.

$$F(N,V,T)=k_BT\mathrm{ln}𝒵$$
(19)
where the canonical partition function $`𝒵`$ is given by:

$`𝒵`$ $`=`$ $`{\displaystyle \frac{1}{s_0^NN!}}{\displaystyle }d𝒓_1\mathrm{}d𝒓_N\mathrm{exp}\{{\displaystyle \frac{1}{k_BT}}[{\displaystyle \underset{i=1}{\overset{N}{}}}Zev_e(𝒓_i)+`$ (21)
$`{\displaystyle \underset{i<j=1}{\overset{N}{}}}[v_C(|𝒓_i𝒓_j|)+v_{hc}(|𝒓_i𝒓_j|)]]\}.`$
Here $`v_e(𝒓_i)`$ is the electrostatic external potential at the position of the particle $`i`$ (in our case, $`v_e(𝒓)`$ is the potential due to the macroion charge), $`v_C(r)=Z^2e^2/Dr`$ is the usual Coulomb part of the pair potential and $`v_{hc}(r)`$ is the hard-core repulsion part:

$$v_{hc}(r)=\{\begin{array}{cc}\mathrm{}\hfill & \text{if }r<2a\hfill \\ 0\hfill & \text{if }r>2a\hfill \end{array},$$
(22)
and $`s_0`$ is the normalizing area. In writing down Eq. (21), we use the primitive model of the solution where all water degrees of freedom are averaged out, resulting in an effective dielectric constant $`D`$ and an effective quantum cell area $`s_0`$.

Substituting Eq. (21) into (19) and differentiating with respect to the particle charge $`e`$, one gets

$$\frac{F}{e}=\frac{2}{e}\left[\underset{i=1}{\overset{N}{}}v_e(𝒓_i)+\underset{i<j=1}{\overset{N}{}}v_C(|𝒓_i𝒓_j|)\right]$$
(23)
here the notation $`\mathrm{}`$ denotes the statistical average.

From Eq. (23), one gets the final expression for the free energy of the system:

$$F=F_0+_0^e\frac{2\mathrm{d}e}{e}\underset{i=1}{\overset{N}{}}v_e(𝒓_i)+\underset{i<j=1}{\overset{N}{}}v_C(|𝒓_i𝒓_j|)$$
(24)
where $`F_0`$ is the free energy of the systems of hard discs with radius $`a`$ at the same concentration. The integration denotes the electrostatic contribution to the free energy. As in the case of a SCL of point charges, because $`\mathrm{\Gamma }`$ is large, one can approximate this electrostatic contribution by that of a Wigner crystal:

$$FF_0+N\epsilon _{WC}(n).$$
(25)
Due to hard-core repulsion, the $`Z`$-ions are never at a distance smaller than $`2a`$ from each other. Therefore, the approximation made in Eq. (25) is even better than that of point charge SCL and is asymptotically exact when $`Aa`$.

Eq. (4) can now be easily obtained by differentiating Eq. (25) with respect to the number of $`Z`$-ions $`N`$.


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# Aging dynamics of quantum spin glasses of rotors

## I Introduction

In recent years the focus of studies of glassy systems has moved from equilibrium to non-equilibrium properties, reflecting the understanding that glassiness is an intrinsically non-equilibrium phenomenon. The effect of quantum mechanics on spin glasses has also been a topic of interest. On the experimental side, there have been several studies of spin systems which are in the vicinity of a quantum phase transition from a spin-glass to a spin-fluid  including the dipolar, transverse-field Ising magnet Li Hox Y1-x F4.  On the theoretical side, studies have mainly focussed on the Ising model in a transverse field or quantum rotors.

There has also been much recent work on the quantum-classical connection in spin glasses,  such as the derivation of quantum TAP equations,  and the large $`N`$ solution of $`SU(N)`$ models of spin glasses.  Quantum fluctuations have been shown to be responsible for redefining the boundary between the spin glass and the quantum disordered phases in systems such as the rotors or the transverse field Ising model. In systems such as the quantum extension of the spherical $`p`$-spin-glass, quantum fluctuations are responsible for a crossover from a second to a first order phase transition.

Another system in which quantum effects and glassiness coexist is in the stripe glasses found in doped Mott insulators (e.g. Ref. ).

In principle, quantum effects could also alter the non-equilibrium dynamics in the glassy regime at very low temperatures. Whilst the properties near the $`T=0`$ quantum critical point of these systems can be understood within a static formulation,  studying the non-equilibrium effects in the glassy system requires a quantum dynamical approach.

Aging effects in classical spin glasses and other glassy systems have been investigated considerably in recent years. The out of equilibrium nature of the system displays itself through a persistent dependence of susceptibilities on the waiting time, the time since the system entered the glassy phase.  The correlation functions in such systems often display quite general scaling features,  and may also have an invariance under time reparametrizations.  It is a natural question to ask whether quantum spin glasses have a similar aging behaviour to their classical counterparts.

Understanding aging dynamics in quantum systems requires formulating the problem within a non-equilibrium closed time path (CTP) formalism, such as the Schwinger-Keldysh approach. This dynamical approach is particularly attractive for studying disordered systems, since it eliminates the need to use replicas in carrying out the average over quenched disorder. This is because the generating functional in the CTP formalism is independent of the disorder realization. Several different disordered quantum systems have been studied recently using this approach, e.g. disordered and interacting electronic systems,  the infinite-range quantum $`p`$-spin glass in the spherical limit,  and a semionic representation for quantum spin systems.

In this paper, using the Schwinger-Keldysh dynamical approach, we investigate the aging behaviour of a spin glass of $`M`$ component quantum rotors that have infinte range interactions and on site self interactions with a coefficient $`u`$. The model of quantum rotors is considerably simpler than that of true quantum Heisenberg spins present in any isotropic antiferromagnet or systems like the doped cuprates; the different components of the rotor variables all commute with each other, unlike the quantum spins. As a consequence, the path-integral written in the rotor variables has an action which contains no Berry phases and is purely real.

The quantum rotors are particularly interesting in elucidating the role of quantum mechanics in the long time dynamics of the glassy phase for a number of reasons. They provide an example of a quantum system with continuous replica symmetry breaking (RSB), in contrast to the one-step RSB quantum $`p`$-spin model with a spherical constraint, which was recently studied by Cugliandolo and Lozano.  Another feature of the rotor system is that it contains an expansion parameter, $`u`$, which we can use to organize a perturbative expansion. When we consider the model to $`O(u)`$, we get equations that look very similar to those obtained in the case of the $`p=2`$ spherical spin model, which has no RSB. However, when we expand to $`O(u^2)`$ we end up with terms that are similar to those from the $`p=4`$ spherical model and also some terms that do not arise in $`p`$-spin models. Therefore, we can investigate very generally how each term contributes to the long time dynamics of the model, and how the quantum effects enter in the problem through each of these terms.

We show that the terms in the dynamical equations that appear as a consequence of quantum mechanics are irrelevant at long times. The precise sense in which the terms are irrelevant was defined in Ref. , using the language of time reparametrization invariance and the reparametrization group (R$`p`$G) of time transformations. Hence, at very long times, the dynamics of the quantum rotors is completely determined by a renormalized classical version of the model. In this time regime, quantum mechanics enters the problem only through a renormalization of the coefficients in the dynamical equations, and there is a complete correspondence between the classical and quantum versions of the model in the aging regime. In particular, this implies that the response and correlation functions of the quantum rotors are related by a modified fluctuation-dissipation relation, with an effective temperature $`T_{\mathrm{eff}}>T`$, just as found in the classical spin glass models. Our results within the R$`p`$G framework extend the connection between the aging regimes of quantum and classical systems, as found in the quantum $`p`$-spin model  with one-step RSB, to a wider and more general class of quantum glassy models.

The paper is organized as follows. In section II, we describe the model that we study and the CTP formalism that we use. In section III we obtain the saddle point dynamical equations for the model and develop the perturbation theory in $`u`$ that we need to obtain these equations. In section IV we study the solutions to these equations in the paramagnetic phase. In section V we investigate the solutions to the dynamical equations in the spin glass phase, and show that a selected number of terms can be made invariant under reparametrizations of the time coordinate in the aging regime. We analyze the terms stemming from the quantum dynamics imposed on the system that are not present in the classical model, and show that they become irrelevant at long times under the time reparametrization transformations. Finally, in section VI we discuss differences between classical and quantum spin glasses.

## II The Model

We consider the model of a glass of quantum rotors introduced in Refs.  with long range interactions on a $`d`$-dimensional lattice with $`N`$ sites. (We let $`d`$ and $`N`$ go to infinity later). An important point to note is that the $`M`$ components of angular momentum of the rotors commute on the same site, unlike Heisenberg spins, for which there are non-trivial commutation relations between the components. This simplification allows us to write a path integral in which there are no Berry phase terms, and makes the rotors much easier to treat analytically.

To derive the dynamical equations, we use a CTP (Schwinger-Keldysh) formalism.  The CTP approach provides a way to study the non-equilibrium response of a system. The price that has to be paid for this is the introduction of a second component to the system, with time flowing in the opposite direction. The non-equilibrium formulation has the advantage that it leads to a generating functional that is automatically normalized to unity. The property of normalization allows averages over disorder realizations in a way that bypasses using replicas.

There are many possibilities for the choice of integration contour in the complex time plane.  The contour $`𝒞`$ that we work with is illustrated in Fig. 1, which starts at $`t=0`$, runs to $`t=\mathrm{}`$, and then returns in the negative $`t`$ direction to $`t=0`$. The contours more usually used, for example in problems involving the calculation of non-linear response, run from $`t=\mathrm{}`$ to $`t=\mathrm{}`$ and back again;  however after an infinite time, the system will have equilibrated, so it is no longer possible to study the non-equilibrium dynamics that we are interested in.

For a system at equilibrium, the usual way to introduce finite temperature is through the density matrix with the form of the Gibbs-Boltzmann distribution. In a non-equilibrium situation, the system cannot be described by the Gibbs-Boltzmann distribution, so an alternative approach is required. The solution is to couple the system to a heat bath  (chosen here to be a set of independent harmonic oscillators) and then allow the system to reach a constant temperature. A detailed account of integrating the bath variables to obtain an effective action in the $`p`$-spin model is given in Ref. , and we follow their approach in our study of the quantum rotors.

### A Effective action for the rotors and bath system

The action for the system of rotors interacting with the bath takes the form

$$S=S_{\mathrm{free}}+S_{\mathrm{int}}+S_{\mathrm{dis}}+S_T,$$
(1)
where $`S_{\mathrm{free}}`$ is the free action, $`S_{\mathrm{int}}`$ describes the self-interaction of the rotors, $`S_{\mathrm{dis}}`$ contains the spin exchange interactions which introduce disorder and frustration to the model, and $`S_T`$ describes the interaction with an external heat bath. The Lagrangian for the free rotors is

$$_{\mathrm{free}}=\underset{i}{}\frac{1}{2g}(_tS_{i\mu }^a)\sigma _3^{ab}(_tS_{i\mu }^b)+\frac{1}{2}m^2S_{i\mu }^a\sigma _3^{ab}S_{i\mu }^b.$$
(2)
The indices on the spin variable $`S_{i\mu }^a`$ refer to the Keldysh contour branch ($`a`$), site ($`i`$), and spin component ($`\mu `$); sums over repeated Keldysh and spin component indices are always implied unless explicitly noted otherwise. The $`\sigma _{1,2,3}`$ are the standard Pauli sigma matrices. Note that the $`S^2`$ terms enter with an opposite sign to the $`S^1`$ terms because the direction of time integration is reversed on the second part of the contour. The first term in the Lagrangian $`_{\mathrm{free}}`$ is a kinetic energy term ($`1/g`$ is the moment of inertia), and the second is a potential energy term ($`m^2`$ also acts as the parameter that tunes between the paramagnetic and spin glass phases) – the free Lagrangian may be thought of as $`M`$-component harmonic oscillators on a lattice, each at site $`i`$.

The self-interactions are described by

$$_{\mathrm{int}}=\underset{i}{}\frac{u}{2}\left\{\left[(S_{i\mu }^1)^2\right]^2\left[(S_{i\mu }^2)^2\right]^2\right\}.$$
(3)
The strength of the self-interaction is $`u`$ and this term is necessary to ensure the stability of the system, since otherwise the Lagrangian would describe randomly coupled harmonic oscillators.

The term in the Lagrangian that contains quenched disorder is

$$_{\mathrm{dis}}=\underset{ij}{}J_{ij}S_{i\mu }^a\sigma _3^{ab}S_{j\mu }^b.$$
(4)
Thermal effects are introduced by placing the system in contact with a heat bath, using the method introduced by Feynman and Vernon.  The contribution of this coupling to the action after integrating out heat bath variables is

$`S_T`$ $`={\displaystyle 𝑑t_1𝑑t_2\underset{i}{}\eta (t_1t_2)S_{i\mu }^a(t_1)[\sigma _1^{ab}+i\sigma _2^{ab}]S_{i\mu }^b(t_2)}`$ (6)
$`+i{\displaystyle 𝑑t_1𝑑t_2\underset{i}{}\nu (t_1t_2)S_{i\mu }^a(t_1)[\delta ^{ab}\sigma _1^{ab}]S_{i\mu }^b(t_2)},`$
where the noise and dissipative kernels, $`\nu `$ and $`\eta `$ respectively, are given by

$`\nu (t)`$ $`={\displaystyle _0^{\mathrm{}}}𝑑\omega I(\omega )\mathrm{coth}\left({\displaystyle \frac{\beta \mathrm{}\omega }{2}}\right)\mathrm{cos}(\omega t),`$ (8)
$`\eta (t)`$ $`=\theta (t){\displaystyle _0^{\mathrm{}}}𝑑\omega I(\omega )\mathrm{sin}(\omega t),`$ (9)
and $`I(\omega )`$ is the spectral density of the bath

$$I(\omega )=\underset{n=1}{\overset{N_b}{}}\delta (\omega \omega _n)\frac{C_n^2}{2M_n\omega _n},$$
(10)
where $`N_b`$ is the number of oscillators in the bath, $`\omega _n`$ is the natural frequency of the $`n^{th}`$ oscillator, $`M_n`$ is its mass, and $`C_n`$ is its coupling to the system. Here we only consider the case of ohmic dissipation

$$I(\omega )=\frac{\gamma }{\pi }\omega e^{\omega /\mathrm{\Lambda }},\mathrm{for}\omega <\mathrm{\Lambda },$$

where $`\gamma `$ plays the role of a friction coefficient (to relate to the notation in previous works,  $`\gamma =M\gamma _0`$).

Properties to note are that both kernels are purely real, $`\nu (t)=\nu (t)`$, and both kernels decay rapidly at large time differences. Note that the quantum fluctuation-dissipation theorem (QFDT) holds for the bath variables when there is ohmic dissipation. The QFDT relating the heat bath variables is

$$\eta (\omega )=\frac{1}{\mathrm{}}\underset{ϵ0}{lim}\frac{d\omega ^{}}{2\pi }\frac{1}{\omega \omega ^{}+iϵ}\mathrm{tanh}\left(\frac{\beta \mathrm{}\omega ^{}}{2}\right)\mathrm{}\nu (\omega ^{}).$$
(11)
### B Disorder average and definition of correlation functions

Having described all of the terms in the action, we now move on to performing the average over disorder realizations and defining the correlation and response in terms of the CTP two-point correlators.

The closed time path generating functional is

$$Z=[DS_{i\mu }^a]e^{\frac{i}{\mathrm{}}S}.$$
(12)
We perform an average over the quenched disorder

$$\overline{Z}=[DJ]𝒫(J_{ij})[DS_{i\mu }^a]e^{\frac{i}{\mathrm{}}S},$$
(13)
where

$$𝒫(J_{ij})=\left(\frac{N}{2\pi J^2}\right)^{\frac{1}{2}}\mathrm{exp}\left[\frac{NJ_{ij}^2}{2J^2}\right],$$
(14)
for a long range interaction. The form Eq. (14) for the disorder probability distribution comes from the assumption that the disorder is Gaussian distributed and that $`\overline{J_{ij}^2}=J^2/N`$ . We can perform the integration over disorder without replicas because of the normalization property of the generating functional in the CTP formulation, since the disorder and the initial conditions are uncorrelated:

$`{\displaystyle [DJ]𝒫(J_{ij})e^{\frac{i}{\mathrm{}}{\scriptscriptstyle 𝑑t_{ij}J_{ij}S_{i\mu }^a(t)\sigma _3^{ab}S_{j\mu }^b(t)}}}=\left({\displaystyle \frac{N}{2\pi J^2}}\right)^{\frac{1}{2}}`$ (15)
$`e^{\frac{J^2}{2N\mathrm{}^2}{\scriptscriptstyle 𝑑t_1𝑑t_2_{ij}\left[S_{i\mu }^a(t_1)\sigma _3^{ab}S_{j\mu }^b(t_1)S_{j\nu }^c(t_2)\sigma _3^{cd}S_{i\nu }^d(t_2)\right]}}.`$ (16)
The dynamical equations are written in terms of the correlation and response, which are defined below. We use an overbar $`\overline{\mathrm{}}`$ to indicate an average over realizations of disorder and angular brackets $`\mathrm{}`$ to indicate an average with respect to the action. The correlation, $`C(t_1,t_2)`$, and response, $`R(t_1,t_2)`$, are

$$C_{ij,\mu \nu }(t_1,t_2)=\frac{1}{2}\overline{S_{i\mu }^1(t_1)S_{j\nu }^1(t_2)+S_{i\mu }^2(t_1)S_{j\nu }^2(t_2)},$$
(18)
and $`R_{ij,\mu \nu }(t_1,t_2)=\delta \overline{S_{i\mu }^1(t_1)}/\delta h_{j\nu }(t_2)`$, which in linear response theory may be written as

$$R_{ij,\mu \nu }(t_1,t_2)=\frac{i}{\mathrm{}}\overline{S_{i\mu }^1(t_1)[S_{j\nu }^1(t_2)S_{j\nu }^2(t_2)]}.$$
(19)
An alternative approach to the dynamics is to introduce a matrix propagator as in the Keldysh formalism,  which takes the form for bosonic fields (e.g. Ref. )

$`G_{ij,\mu \nu }^{11}(t_1,t_2)`$ $`=`$ $`i𝒯\left[S_{i\mu }^1(t_1)S_{j\nu }^1(t_2)\right],`$ (20)
$`G_{ij,\mu \nu }^{12}(t_1,t_2)`$ $`=`$ $`iS_{j\nu }^2(t_2)S_{i\mu }^1(t_1),`$ (21)
$`G_{ij,\mu \nu }^{21}(t_1,t_2)`$ $`=`$ $`iS_{i\mu }^2(t_1)S_{j\nu }^1(t_2),`$ (22)
$`G_{ij,\mu \nu }^{22}(t_1,t_2)`$ $`=`$ $`i\stackrel{~}{𝒯}\left[S_{i\mu }^2(t_1)S_{j\nu }^2(t_2)\right],`$ (23)
where $`𝒯`$ and $`\stackrel{~}{𝒯}`$ are the operators for time ordering and anti-time ordering respectively. Under the transformation in Keldysh space $`G\widehat{G}=LGL^{}`$, where

$$L=\frac{1}{\sqrt{2}}(\mathrm{𝟏}i\sigma _2),$$
(24)
the propagator takes the form

$`\widehat{G}=LGL^{}=\left(\begin{array}{cc}0& G^A\\ G^R& G^K\end{array}\right),`$ (25)
where

$`G^R`$ $`=`$ $`G^{11}G^{12}=G^{21}G^{22},`$ (26)
$`G^A`$ $`=`$ $`G^{11}G^{21}=G^{12}G^{22},`$ (27)
$`G^K`$ $`=`$ $`G^{11}+G^{22}=G^{21}+G^{12},`$ (28)
and the results follow from the definitions of the propagators in terms of time ordered products. The definitions above imply the following properties for the propagators

$`G_{ji,\nu \mu }^R(t_2,t_1)`$ $`=`$ $`G_{ij,\mu \nu }^A(t_1,t_2),`$ (29)
$`G_{ji,\nu \mu }^K(t_2,t_1)`$ $`=`$ $`G_{ij,\mu \nu }^K(t_1,t_2).`$ (30)
The retarded and advanced propagators are purely real and the Keldysh propagator is purely imaginary. Under the transformation, $`L`$, the spins are also rotated, $`S\stackrel{~}{S}=LS`$, so for

$$S=\left(\begin{array}{c}S^1\\ S^2\end{array}\right),$$
(31)
we have

$$\stackrel{~}{S}=\frac{1}{\sqrt{2}}\left(\begin{array}{c}S^1S^2\\ S^1+S^2\end{array}\right)=\left(\begin{array}{c}\widehat{S}\\ S\end{array}\right).$$
(32)
The $`\widehat{S}`$ and $`S`$ variables in the quantum CTP formulation naturally become the usual variables within the Martin-Siggia-Rose (MSR) formalism  when the classical limit is taken. The relation between the Keldysh and retarded propagators and the correlation and response is

$`G^K(t_1,t_2)`$ $`=`$ $`2iC(t_1,t_2),`$ (33)
$`G^R(t_1,t_2)`$ $`=`$ $`\mathrm{}R(t_1,t_2).`$ (34)
We will work with the correlation and response rather than the propagators in the dynamical equations. However, it is easier to use the matrix propagator in the Feynman rules for including interactions, rather than using a diagrammatic technique where response and correlation are treated differently.

In anticipation of the saddle-point evaluation for the disorder term, we perform a Hubbard-Stratonovich transformation to decouple the four spin term generated by the disorder average. Introducing the Hubbard-Stratonovich field $`Q_{ij,\mu \nu }^{ab}(t_1,t_2)`$, the effective action can be rewritten as

$`Z`$ $`=`$ $`{\displaystyle [DQ]e^{\frac{N}{2J^2}{\scriptscriptstyle 𝑑t_1𝑑t_2_iQ_{i,\nu \mu }^{ba}(t_2,t_1)Q_{i,\mu \nu }^{ab}(t_1,t_2)}}Z[Q]},`$ (35)
$`Z[Q]`$ $`=`$ $`{\displaystyle [D\stackrel{~}{S}]e^{\frac{i}{\mathrm{}}S_{\mathrm{free}}+\frac{i}{\mathrm{}}S_Q+\frac{i}{\mathrm{}}S_{\mathrm{int}}+\frac{i}{\mathrm{}}S_T}},`$ (36)
where

$`S_{\mathrm{free}}`$ $`=`$ $`{\displaystyle 𝑑t\underset{i}{}\stackrel{~}{S}_{i\mu }^a(t)\mathrm{\Gamma }_{\mu \nu }^{ab}\stackrel{~}{S}_{i\nu }^b(t)},`$ (37)
$`S_Q`$ $`=`$ $`{\displaystyle 𝑑t_1𝑑t_2\underset{i}{}Q_{i,\mu \nu }^{ab}(t_1,t_2)\stackrel{~}{S}_{i\mu }^a(t_1)\sigma _1^{bc}\stackrel{~}{S}_{i\nu }^c(t_2)}.`$ (38)
Next we introduce a modified version of the Hubbard-Stratonovich field, $`\stackrel{~}{Q}_{i,\mu \nu }^{ab}=Q_{i,\mu \nu }^{ac}\sigma _1^{cb}`$, thus

$`Z`$ $`=`$ $`{\displaystyle [D\stackrel{~}{Q}]e^{\frac{N}{2J^2}{\scriptscriptstyle 𝑑t_1𝑑t_2_i\sigma _1^{a^{}a}\sigma _1^{bb^{}}\stackrel{~}{Q}_{i,\nu \mu }^{b^{}a^{}}(t_2,t_1)\stackrel{~}{Q}_{i,\mu \nu }^{ab}(t_1,t_2)}}}`$ (40)
$`\times {\displaystyle }[D\stackrel{~}{S}]e^{\frac{i}{\mathrm{}}S_{\mathrm{free}}+\frac{i}{\mathrm{}}S_{\stackrel{~}{Q}}+\frac{i}{\mathrm{}}S_{\mathrm{int}}+\frac{i}{\mathrm{}}S_T},`$
where

$`S_{\stackrel{~}{Q}}={\displaystyle 𝑑t_1𝑑t_2\underset{i}{}\stackrel{~}{Q}_{i,\mu \nu }^{ab}(t_1,t_2)\stackrel{~}{S}_{i\mu }^a(t_1)\stackrel{~}{S}_{i\nu }^b(t_2)}.`$ (41)
The $`\stackrel{~}{\mathrm{\Gamma }}_{\mu \nu }^{ab}`$ term has the structure

$`\stackrel{~}{\mathrm{\Gamma }}_{\mu \nu }^{ab}=\delta _{\mu \nu }\left(\begin{array}{cc}\mathrm{\Gamma }_K& \mathrm{\Gamma }_R\\ \mathrm{\Gamma }_A& 0\end{array}\right),`$ (42)
where

$$\mathrm{\Gamma }_R=\mathrm{\Gamma }_A=\frac{1}{2g}\frac{^2}{t^2}+\frac{1}{2}m^2,\mathrm{\Gamma }_K=0.$$
(43)
## III Dynamical equations

Using propagators, the self-consistent mean field equations can be represented in the form

$$G^1=G_0^1\mathrm{\Sigma }_J\mathrm{\Sigma }_T\mathrm{\Sigma }_u,$$
(44)
where the $`\mathrm{\Sigma }`$ terms are the self energies from the disorder, the interaction with the thermal bath and from self-interaction respectively. The general strategy that we will adopt in obtaining the dynamical equations for this model is to perform a saddle point evaluation of $`\mathrm{\Sigma }_J`$ and then a perturbation expansion in $`u`$. We obtain a solution to $`O(u)`$ in the paramagnetic phase, in analogy with the replica symmetric solution in the equilibrium problem,  whilst in the spin glass phase we need to consider terms to $`O(u^2)`$ in the interaction, which are the terms found to contribute to RSB.

### A Saddle point evaluation of $`\mathrm{\Sigma }_J`$

At the saddle point the functional derivative with respect to the Hubbard-Stratonovich field is zero

$$\frac{\delta Z}{\delta Q}=0.$$

The variation leads to the following equations

$`0`$ $`=`$ $`{\displaystyle \frac{N\mathrm{}i}{2J^2}}\sigma _1^{bb^{}}\stackrel{~}{Q}_{\nu \mu }^{b^{}a^{}}(t_2,t_1)\sigma _1^{a^{}a}`$ (46)
$`+{\displaystyle \underset{i}{}}\stackrel{~}{S}_{i\mu }^a(t_1)\stackrel{~}{S}_{i\nu }^b(t_2).`$
Rearranging gives

$$\stackrel{~}{Q}_{\mu \nu }^{ab}(t_1,t_2)=\frac{2J^2}{\mathrm{}}\sigma _1^{bb^{}}G_{\nu \mu }^{b^{}a^{}}(t_2,t_1)\sigma _1^{aa^{}}.$$
(47)
By substituting the saddle solution into Eq. (41), one obtains the self-energy contribution coming from the disorder:

$`\mathrm{\Sigma }_J(t_1,t_2)=`$ $`{\displaystyle \frac{2J^2}{\mathrm{}}}\sigma _1G(t_1,t_2)\sigma _1`$ (48)
$`=`$ $`{\displaystyle \frac{2J^2}{\mathrm{}}}\left(\begin{array}{cc}G^K& G^R\\ G^A& 0\end{array}\right)_{(t_1,t_2)}.`$ (49)
The notation of a matrix with $`(t_1,t_2)`$ following it is used to indicate that all of the propagators in the matrix have that as their argument. At the mean field level the solution is homogeneous in the site index, so we drop it. In the absence of a magnetic field, we also drop the spin indicies, i.e. $`G_{\mu \nu }=G\delta _{\mu \nu }`$.

### B Diagrammatic perturbation in $`u`$

The interaction terms in the action may be treated in a diagrammatic way by noting that in the $`\stackrel{~}{S}`$ basis, the interaction term is written as

$$S_{\mathrm{int}}=\frac{u}{2}_0^{\mathrm{}}𝑑t\underset{i}{}\stackrel{~}{S}_{i\mu }^a(t)\stackrel{~}{S}_{i\nu }^a(t)\stackrel{~}{S}_{i\mu }^c(t)\sigma _1^{cd}\stackrel{~}{S}_{i\nu }^d(t).$$
(50)
The Feynman rules (see Fig. 2) for calculating $`\mathrm{\Sigma }_u`$ term by term in $`u`$ are that the propagator (solid line) is $`iG_{\mu \nu }^{ab}(t,t^{})`$ and the interaction propagator (dashed line with a dot at one end) is $`i\frac{u}{2}\sigma _1^{ab}\delta ^{cd}\delta _{\mu \nu }`$. The $`\sigma _1`$ is inserted at the end with the dot.

This leads to four contributions to the self energy $`\mathrm{\Sigma }_u`$ to first order in $`u`$, as shown in Fig. 3. Note that the bottom two diagrams in Fig. 3 are proportional to $`M`$, the number of spin components of the rotors, since there is a trace around a closed loop, and that the trace includes spin indicies. Note also that $`tr(G\sigma _1)=0`$, since $`G^R(t,t)=0`$. The sum of these contributions is

$`\mathrm{\Sigma }_u^{(1)}(t,t^{})`$ $`=`$ $`{\displaystyle \frac{iu}{2}}(1+M)\sigma _1G^K(t,t)\delta (tt^{}),`$ (51)
where the superscript (1) indicates that the self energy is to first order in $`u`$.

To second order in $`u`$ there are six different one particle irreducible diagram topologies to consider which contribute to the self energy and four different diagrams for each topology (the different topologies are shown in Fig. 4). We treat each topology separately, starting with the propagator with two self interactions, which contributes

$`\mathrm{\Sigma }_u^{(2a)}(t,t^{})={\displaystyle \frac{u^2}{8\mathrm{}}}\times `$ (52)
$`\left(\begin{array}{cc}[3(G^A)^2+3(G^R)^2+(G^K)^2]G^K& [3(G^K)^2+(G^A)^2]G^A\\ [3(G^K)^2+(G^R)^2]G^R& 0\end{array}\right)_{(t,t^{})}.`$ (53)
The next diagrams are the vertex correction to the closed loop that contributes to $`\mathrm{\Sigma }_u^{(1)}`$ and the propagator with one self interaction, which contribute

$`\mathrm{\Sigma }_u^{(2b)}(t,t^{})`$ $`=`$ $`{\displaystyle \frac{u^2}{4\mathrm{}}}\sigma _1\delta (tt^{})`$ (55)
$`\times \left[{\displaystyle _0^{\mathrm{}}}𝑑\stackrel{~}{t}G^K(\stackrel{~}{t},\stackrel{~}{t})G^R(t,\stackrel{~}{t})G^K(t,\stackrel{~}{t})\right].`$
The remainder of the self energies are expressible in terms of the expressions found in equations (52) and (55): $`\mathrm{\Sigma }^{(2c)}=M\mathrm{\Sigma }^{(2a)}`$, $`\mathrm{\Sigma }^{(2d)}=M\mathrm{\Sigma }^{(2b)}`$, $`\mathrm{\Sigma }^{(2e)}=\mathrm{\Sigma }^{(2b)}`$ and $`\mathrm{\Sigma }^{(2f)}=\mathrm{\Sigma }^{(2d)}`$. The diagram that plays the most important role in the physics is (2a) because it depends on two times rather than only one.

### C The dynamical equations

From the self consistent Eq. (44) we obtain the dynamical equation

$$\mathrm{𝟏}=\left(G_0^1\mathrm{\Sigma }_J\mathrm{\Sigma }_T\mathrm{\Sigma }_u\right)G.$$
(56)
By substituting the self-energies $`\mathrm{\Sigma }_J`$, $`\mathrm{\Sigma }_T`$ and $`\mathrm{\Sigma }_u`$ that we determined above to order $`u^2`$, and shifting notation to response and correlation, we obtain the dynamical equations for the quantum rotor model

$`\delta (t_1t_2)`$ $`=`$ $`\{{\displaystyle \frac{1}{2g}}{\displaystyle \frac{^2}{t_1^2}}{\displaystyle \frac{1}{2}}m^2u(1+M)C(t_1,t_1)`$ (63)
$`2(1+M)u^2C(t_1,t_1)`$
$`\times {\displaystyle _0^{\mathrm{}}}dtR(t_1,t)C(t_1,t)\}R(t_1,t_2)`$
$`+{\displaystyle _0^{\mathrm{}}}𝑑t\eta (t_1t)R(t,t_2)`$
$`2J^2{\displaystyle _0^{\mathrm{}}}𝑑tR(t_1,t)R(t,t_2)`$
$`{\displaystyle \frac{3}{2}}(1+M)u^2{\displaystyle _0^{\mathrm{}}}𝑑tC(t_1,t)^2R(t_1,t)R(t,t_2)`$
$`+{\displaystyle \frac{1}{2}}(1+M)u^2\mathrm{}^2{\displaystyle _0^{\mathrm{}}}𝑑tR(t_1,t)^3R(t,t_2),`$
and

$`0`$ $`=`$ $`\{{\displaystyle \frac{1}{2g}}{\displaystyle \frac{^2}{t_1^2}}{\displaystyle \frac{1}{2}}m^2u(1+M)C(t_1,t_1)`$ (71)
$`2(1+M)u^2C(t_1,t_1){\displaystyle _0^{\mathrm{}}}dtR(t_1,t)C(t_1,t)\}C(t_1,t_2)`$
$`+{\displaystyle _0^{\mathrm{}}}𝑑t\eta (t_1t)C(t,t_2){\displaystyle \frac{\mathrm{}}{2}}{\displaystyle _0^{\mathrm{}}}𝑑t\nu (t_1t)R(t_2,t)`$
$`2J^2{\displaystyle _0^{\mathrm{}}}𝑑t\left[C(t_1,t)R(t_2,t)+R(t_1,t)C(t,t_2)\right]`$
$`{\displaystyle \frac{1}{2}}(1+M)u^2{\displaystyle _0^{\mathrm{}}}𝑑tC(t_1,t)^3R(t_2,t)`$
$`{\displaystyle \frac{3}{2}}(1+M)u^2{\displaystyle _0^{\mathrm{}}}𝑑tC(t_1,t)^2R(t_1,t)C(t,t_2)`$
$`+{\displaystyle \frac{1}{2}}(1+M)u^2\mathrm{}^2{\displaystyle _0^{\mathrm{}}}dt[R(t_1,t)^3C(t,t_2)`$
$`+3R(t_1,t)^2R(t_2,t)C(t_1,t)].`$
The terms that arise in this expansion look partly like a $`p=4`$ spherical spin glass (the $`C^3R`$ term in the correlation equation), but there are also terms (multiplied by $`\mathrm{}^2`$) which do not appear in the classical spherical model.

## IV Paramagnetic phase

In the paramagnetic phase the correlation and response are time translation invariant (TTI) after the initial transients have died out. We find a solution to the dynamical equations (63) and (71) to $`O(u)`$ in this phase. With the assumption of TTI correlators, let $`\tau =t_1t_2`$, and then let $`t_1\mathrm{}`$. Define $`C_{\mathrm{}}=lim_{t_1\mathrm{}}C(t_1,t_1)`$, which is the equilibrium limit of the equal time correlation (we also use $`C_{\mathrm{}}`$ in the spin glass phase; as a one time quantity the equal time correlation has a limit as $`t_1\mathrm{}`$). TTI allows us to solve the problem in the paramagnetic phase by performing a Fourier transformation:

$`1`$ $`=`$ $`\left\{{\displaystyle \frac{\omega ^2}{2g}}+{\displaystyle \frac{1}{2}}m^2+u(1+M)C_{\mathrm{}}\right\}R(\omega )`$ (74)
$`+i{\displaystyle _{\mathrm{}}^{\mathrm{}}}{\displaystyle \frac{d\omega ^{}}{2\pi }}{\displaystyle \frac{R(\omega ^{})\eta (\omega ^{})}{\omega \omega ^{}+i0}}`$
$`2J^2i{\displaystyle _{\mathrm{}}^{\mathrm{}}}{\displaystyle \frac{d\omega ^{}}{2\pi }}{\displaystyle \frac{R(\omega ^{})R(\omega ^{})}{\omega \omega ^{}+i0}},`$
and

$`0`$ $`=`$ $`\left\{{\displaystyle \frac{\omega ^2}{2g}}+{\displaystyle \frac{1}{2}}m^2+u(1+M)C_{\mathrm{}}\right\}C(\omega )`$ (78)
$`+i{\displaystyle _{\mathrm{}}^{\mathrm{}}}{\displaystyle \frac{d\omega ^{}}{2\pi }}{\displaystyle \frac{\eta (\omega ^{})C(\omega ^{})}{\omega \omega ^{}+i0}}`$
$`{\displaystyle \frac{\mathrm{}}{2}}i{\displaystyle _{\mathrm{}}^{\mathrm{}}}{\displaystyle \frac{d\omega ^{}}{2\pi }}{\displaystyle \frac{\nu (\omega ^{})R(\omega ^{})}{\omega \omega ^{}+i0}}`$
$`2J^2i{\displaystyle _{\mathrm{}}^{\mathrm{}}}{\displaystyle \frac{d\omega ^{}}{2\pi }}\left[{\displaystyle \frac{C(\omega ^{})R(\omega ^{})+R(\omega ^{})C(\omega ^{})}{\omega \omega ^{}+i0}}\right].`$
The following properties hold for the correlation and reponse and their Fourier transforms: $`C(t)`$ is invariant under time reversal and is real, hence $`C(\omega )=C^{}(\omega )`$, $`C^{}(\omega )=C(\omega )`$ and $`C(\omega )`$ is real. The response is real, hence $`R(\omega )+R(\omega )=2\mathrm{Re}[R(\omega )]`$ and $`R(\omega )R(\omega )=2i\mathrm{Im}[R(\omega )]`$. In addition, the noise kernel $`\nu (\omega )`$ is real and has the property $`\nu (\omega )=\nu (\omega )`$. The real part of the equation (78) combined with the QFDT for the heat bath variables (11) gives

$$\mathrm{Im}[R(\omega )]=\frac{1}{\mathrm{}}\mathrm{tanh}\left(\frac{\beta \mathrm{}\omega }{2}\right)C(\omega ).$$
(79)
Hence the correlation and response are related by the QFDT if the same is true for the heat bath variables. In this regime, we can solve explicity for the response, and hence the correlation through the QFDT (79). We use these solutions to investigate the self-consistency condition in the paramagnetic regime and investigate critical slowing down as discussed by Sompolinsky.

### A Response, correlation, and phase boundary

Assuming that the integrands in the resonant integrals in equations (74) and (78) fall off sufficiently quickly at large $`\omega `$, then they may be rewritten and solved for $`R(\omega )`$ to give

$$R(\omega )=\frac{x(\omega )}{4J^2}\frac{1}{4J^2}\sqrt{x(\omega )^28J^2},$$
(80)
where

$$x(\omega )=\frac{\omega ^2}{2g}+\frac{1}{2}m^2+u(1+M)C_{\mathrm{}}\eta (\omega ),$$

(note that $`\eta (\omega )`$ has both real and imaginary parts). In the limit that $`\omega 0`$, the real part of the kernel $`\eta `$ is proportional to the frequency cutoff, $`\mathrm{\Lambda }`$, so to remove this, define $`m_1^2=m^22\eta (0)`$. Then at zero frequency at the critical point,

$$\frac{1}{2}m_1^2+u(1+M)C_{\mathrm{}}=2\sqrt{2}J,$$
(81)
and the imaginary part of the response is

$`\mathrm{Im}[R(\omega )]`$ $`=`$ $`{\displaystyle \frac{\mathrm{Im}[\eta (\omega )]}{4J^2}}`$ (83)
$`{\displaystyle \frac{1}{4J^2}}\sqrt{2\left|\mathrm{Im}[\eta (\omega )]\right|\sqrt{\mathrm{Im}[\eta (\omega )]^2+8J^2}}.`$
To get the self-consistency condition for $`C_{\mathrm{}}`$ at the critical point, we use equation (83) and the QFDT

$$C_{\mathrm{}}=\mathrm{}_{\mathrm{}}^{\mathrm{}}\frac{d\omega }{2\pi }\mathrm{coth}\left(\frac{\beta \mathrm{}\omega }{2}\right)\mathrm{Im}[R(\omega )].$$
(84)
Using

$$\mathrm{Im}[\eta (\omega )]=\frac{\gamma \omega }{2}e^{|\omega |/\mathrm{\Lambda }}\theta (\mathrm{\Lambda }|\omega |),$$
(85)
and noting that the second integral vanishes, since the integrand is odd, we get the result

$$C_{\mathrm{}}=\frac{\pi \gamma }{48\mathrm{}\beta ^2J^2}+O(\mathrm{\Lambda }^2).$$
(86)
The quantity $`C_{\mathrm{}}`$ fixes the equal-time correlation, and provides a constraint for the rotor size in this model, since we do not impose a spherical constraint.  In the spin glass phase $`C(t,t)`$ should relax to an equilibrium value, $`q`$, the Edwards-Anderson order parameter.  This is because it is a one time quantity – the same is not true for two time quantities. The quantity $`m_1^2`$ acts to “tune” the system through the spin glass transition. Using equation (81) and separating $`m_1^2`$ into a piece that depends on the cutoff and a temperature dependent piece, we have an expression analagous to the one found for $`r_C(T)`$ in the equilibrium study of quantum rotors

$$m_1^2(\beta )=m_1^2\frac{u(1+M)\gamma }{24\mathrm{}\beta ^2J^2}.$$
(87)
### B Critical slowing down

The dynamic transition from the paramagnetic to the spin glass phase was investigated by Sompolinsky and Zippelius.  However, in their treatment they took the infinite time limit before, rather than after the $`N\mathrm{}`$ limit, the opposite order of limits than that considered here. This leads to finite energy barriers between traps and hence an infinite hierachy of time scales and an ergodic solution. In the situtation we consider the system is confined to a single ergodic component and we are studying the relaxation within a trap.

To connect with the work of Sompolinsky and Zippelius, define

$`\mathrm{\Gamma }^1(\omega )={\displaystyle \frac{}{\omega }}R^1(\omega ),`$ (88)
which leads to $`\mathrm{\Gamma }(\omega )1/\omega `$ at small frequencies and

$$\mathrm{\Gamma }^1(\omega )=\frac{\frac{\eta }{\omega }\frac{\omega }{g}}{\left(12J^2R(\omega )^2\right)},$$
(89)
which is analagous to their result.

### C Alternative approach – Schwinger-Keldysh Landau Theory

In previous work on quantum rotor systems,  the approach taken has been to obtain a replicated field theory in the Hubbard-Stratonovich $`Q`$ fields. In this and related work,  we have obtained directly dynamical equations for spin correlation functions. In the following we will briefly show how to set up a Landau theory for the fields $`Q`$ within a completely dynamical approach, and connect to both the replica results of Ref.  and the results obtained in the preceeding sections.

In the dynamical Schwinger-Keldysh approach, if the system does reach equilibrium with the bath (as is the case in the paramagnetic phase), then the temperature of the heat bath can be introduced through the use of a density matrix rather than with the heat bath kernels referred to in the previous section.

Just as in section II, integrating over disorder and introducing a Hermitian Hubbard-Stratonovich field leads to the following action

$`Z={\displaystyle [D\stackrel{~}{Q}]e^{\frac{1}{2J^2}{\scriptscriptstyle 𝑑t_1𝑑t_2_{ij}\stackrel{~}{Q}_i\sigma _1K_{ij}^1\stackrel{~}{Q}_j\sigma _1}\mathrm{log}Z_0[\stackrel{~}{Q}]}},`$ (90)
where $`Z_0`$ is the single site generating functional

$`Z_0[\stackrel{~}{Q}]`$ $`={\displaystyle 𝒟S^a\mathrm{exp}[iS_0]},`$ (91)
$`S_0`$ $`=S_{\mathrm{free}}+S_{\mathrm{nl}}`$ (93)
$`{\displaystyle 𝑑t𝑑t^{}\underset{i}{}\stackrel{~}{Q}_{i\mu \nu }^{ab}(t,t^{})S_{i\nu }^b(t^{})S_{i\mu }^a(t)},`$
where $`S_{\mathrm{nl}}`$ includes the self-interactions and interaction with the bath. We can expand $`Z_S[\stackrel{~}{Q}]`$ by obtaining the perturbative vertices in powers of the $`\stackrel{~}{Q}`$ fields, noting that the mean-field solution is isotropic in space. Using standard diagrammatic methods and in simplified notation, the effective action up to the cubic order is

$`S`$ $`=`$ $`{\displaystyle \frac{d\omega }{2\pi }Tr(QG_0)}+{\displaystyle \frac{d\omega _1}{2\pi }\frac{d\omega _2}{2\pi }Tr(QG_0)^2}`$ (98)
$`+{\displaystyle \frac{d\omega _1}{2\pi }\frac{d\omega _2}{2\pi }\frac{d\omega _3}{2\pi }Tr(QG_0)^3}`$
$`iu{\displaystyle \frac{d\omega _1}{2\pi }\frac{d\omega _2}{2\pi }\frac{d\omega _3}{2\pi }Tr[(G_0QG_0)\sigma _1(G_0QG_0)]}`$
$`iu{\displaystyle \frac{d\omega _1}{2\pi }\frac{d\omega _2}{2\pi }\frac{d\omega _3}{2\pi }Tr(G_0QG_0)}`$
$`Tr(\sigma _1G_0QG_0)+\mathrm{},`$
where $`\mathrm{}`$ means higher order terms. It is important to point out that terms with coefficient $`u`$ are important to get stable saddle point solutions. We study the saddle point solutions in the absence of spatial fluctuations.

Consider the following saddle point solution which is $`O(M)`$ and TTI:

$`Q_{\mu \nu }^{ab}(\omega _1,\omega _2)`$ $`=`$ $`2\pi \delta (\omega _1+\omega _2)\delta _{\mu \nu }Q^{ab}(\omega _1),`$ (99)
$`Q`$ $`=`$ $`\left(\begin{array}{cc}Q_K& Q_R\\ Q_A& 0\end{array}\right).`$ (100)
This Ansatz has the same structure in frequency and $`O(M)`$ indices as in the replica approach.  However, here we are dealing with a $`2\times 2`$ matrix in Keldysh space in contrast to the $`n\times n`$ ( $`n0`$ limit ) replica matrix. This leads to the saddle point action

$`S_{\mathrm{sp}}`$ $`=`$ $`{\displaystyle \frac{d\omega }{2\pi }(Q_RG_R^0+Q_AG_A^0)}`$ (103)
$`+{\displaystyle \frac{d\omega }{2\pi }[(Q_RG_R^0)^2+(Q_AG_A^0)^2]}`$
$`+{\displaystyle \frac{d\omega }{2\pi }[(Q_RG_R^0)^3+(Q_AG_A^0)^3]}`$
$``$ $`iu(1+M){\displaystyle \frac{d\omega }{2\pi }[Q_R(G_R^0)^2+Q_A(G_A^0)^2]}`$ (105)
$`\times {\displaystyle }{\displaystyle \frac{d\omega }{2\pi }}[(Q_RG_R^0+Q_AG_A^0)G_K^0+Q_KG_R^0G_A^0]`$
$`+`$ $`\mathrm{}.`$ (106)
By using the analytic properties of retarded and advanced Green functions, we can remove the quadratic term by a shift $`Q(\omega )Q(\omega )C\mathrm{\Gamma }(\omega )`$. In the low energy limit, using free propagators: $`G_R^0G_A^0\omega ^2r,G_K^00`$, we get:

$`S_{\mathrm{sp}}`$ $`=`$ $`{\displaystyle \frac{d\omega }{2\pi }(\omega ^2r)(Q_R+Q_A)}+{\displaystyle \frac{\kappa }{3}}{\displaystyle \frac{d\omega }{2\pi }[Q_R^3+Q_A^3]}`$ (107)
$``$ $`iu(1+M){\displaystyle \frac{d\omega }{2\pi }[Q_R+Q_A]\frac{d\omega }{2\pi }Q_K}+\mathrm{}.`$ (108)
#### Solution in the Paramagnetic phase

Minimizing Equation (108) with respect to $`Q_R`$ and $`Q_A`$, gives

$`\omega ^2r+Q_R^2iu(1+M){\displaystyle \frac{d\omega }{2\pi }Q_K}=0,`$ (109)
$`\omega ^2r+Q_A^2iu(1+M){\displaystyle \frac{d\omega }{2\pi }Q_K}=0.`$ (110)
The two equations are complex conjugates of each other, therefore there is only one independent equation. Solving for $`Q_R`$ gives

$`Q_R^2`$ $`=`$ $`(\omega ^2\stackrel{~}{r}),`$ (111)
$`\stackrel{~}{r}`$ $`=`$ $`ru(1+M){\displaystyle \frac{d\omega }{2\pi }\mathrm{coth}\frac{\beta \omega }{2}\chi ^{\prime \prime }(\omega )},`$ (112)
$`\chi ^{\prime \prime }(\omega )`$ $`=`$ $`\mathrm{sgn}(\omega )(\omega ^2\stackrel{~}{r})^{1/2}\theta (\omega \sqrt{\stackrel{~}{r}}).`$ (113)
The critical point is located at $`\stackrel{~}{r}=0`$ where $`r=r_c(T)=u(1+M)\frac{d\omega }{2\pi }\omega \mathrm{coth}\frac{\beta \omega }{2}`$. These results are the same as those obtained by the replica approach in Ref..

## V Glassy Phase

In the spin glass phase the correlation and response are no longer time translation invariant. Instead, there is an aging piece that remains a function of two times. Below we investigate the dynamical behavior of the correlation and response functions for the quantum rotors in the glassy phase.

### A Weak ergodicity breaking and weak long term memory

Weak ergodicity breaking (WEB) and weak long term memory (WLTM) are phenomena that have been observed in the solutions to classical mean field spin glass models.  The numerical results for the quantum version of the $`p`$-spin model  are in agreement with those predicted from these scenarios, and we also assume WEB and WLTM in our solution of the quantum rotor model.

WEB can be summarized as follows: the correlation function behaves as the sum of a TTI piece and a piece which depends on two times

$$C(t_1,t_2)=C_{ST}(t_1t_2)+C_{AG}(t_1,t_2).$$
(114)
The stationary (TTI) piece decays to zero as $`t_1t_2\mathrm{}`$, and the aging piece satisfies $`C_{AG}(t,t)=q`$, and

$$\underset{t_1\mathrm{}}{lim}C_{AG}(t_1,t_2)=0,$$
(115)
so that both times are important in the decay of the aging piece of the correlation. We separate the response in a similar way to the correlation

$`R(t_1,t_2)`$ $`=`$ $`R_{ST}(t_1t_2)+R_{AG}(t_1,t_2),`$ (116)
The stationary piece decays to zero as $`t_1t_2\mathrm{}`$, whilst the decay of the aging piece depends on both times. The assumption of WLTM applies to the integral of the response function: the integral of the response over any finite time interval vanishes, i.e.

$$\underset{t_1\mathrm{}}{lim}_0^t𝑑t_2R(t_1,t_2)=0,$$
(117)
for fixed $`t`$, however the integral over an interval that grows with time is finite

$$\underset{t_1\mathrm{}}{lim}_0^{t_1}𝑑t_2R(t_1,t_2)0.$$
(118)
### B Modified QFDT

Treating the spin glass regime in a similar way to the paramagnetic phase, and looking in the limit $`t_1\mathrm{}`$, it is possible to get an equation that includes the TTI pieces, and also some static pieces due to a non-zero Edwards-Anderson order parameter.

In the spin glass phase, we need to take into account the aging that has occurred up until the waiting time.  To do this we split $`R`$ and $`C`$ into stationary and aging pieces before letting $`t_1\mathrm{}`$ and then Fourier transforming. The relation we find between the stationary parts of correlation and response is

$`\mathrm{Im}[R_{ST}(\omega )]`$ $`=`$ $`{\displaystyle \frac{1}{\mathrm{}}}\mathrm{tanh}\left({\displaystyle \frac{\beta \mathrm{}\omega }{2}}\right)C_{ST}(\omega )`$ (120)
$`+{\displaystyle \frac{2\pi \beta J^2}{\gamma }}q\left(\chi _{\mathrm{}}+(RC)_{\mathrm{}}\right)\delta (\omega ),`$
where

$$\chi _{\mathrm{}}=\underset{t_1\mathrm{}}{lim}_0^{t_1}𝑑tR_{ST}(t_1t),$$
(121)
and $`(RC)_{\mathrm{}}`$ is (noting that $`t_1t_2|t_1t_2|`$ in the evaluation of the integral)

$$(RC)_{\mathrm{}}=\underset{t_1\mathrm{}}{lim}_0^{t_1}𝑑tR_{AG}(t_1,t)\left(C_{AG}(t,t_1)+C_{AG}(t_1,t)\right).$$
(122)
Equation (120) shows how the QFDT is modified in the spin glass phase for the rotor model. There is the usual piece that is present in the paramagnetic phase, and then a delta function at zero frequency that grows with decreasing temperature.

#### Modified QFDT within the dynamical Landau theory

As in the treatment above, in the spin glass state, the Keldysh component $`Q_K`$ acquires a non-trivial $`\delta `$ function part due to a nonzero Edwards-Anderson order parameter

$$iQ_K=iQ_K^{reg}+2\pi q\delta (\omega ).$$
(123)
Substituting the ansatz into Equation (110) gives

$$\omega ^2r+Q_R^2iu(1+M)\frac{d\omega }{2\pi }Q_K^{reg}(u+Mv)q=0,$$
(124)
and solving for $`Q_R`$ and $`q`$ leads to

$`Q_R`$ $`=`$ $`i\omega ,`$ (125)
$`q`$ $`=`$ $`{\displaystyle \frac{1}{u(1+M)}}(r_c(T)r).`$ (126)
Again, these results are the same as those obtained by the replica approach in Ref..

### C Aging regime

Aging behaviour has been shown to be a feature in the long time dynamics of many glassy systems, both in experiments  and theoretical models (see Ref.  for a review). In the case of spin glasses, the major models that have been studied in the aging regime are the Sherrington Kirkpatrick  (SK) model, the spherical $`p`$-spin model,  and the quantum version of the spherical $`p`$-spin model.  In our work we consider the quantum version of the rotor model, which in the absence of a magnetic field, is similar to the soft spin SK model with quantum dynamics rather than Langevin dynamics, having $`M`$ components instead of only one.

One of the features of equilibrium solutions of mean field spin glass models is replica symmetry breaking, introduced by Parisi  in the context of the SK model. Cugliandolo and Kurchan  started from a set of equations for the long time dynamics of the SK model and showed that the correlations have an ultrametric structure analagous to that found in the Parisi RSB solution of the SK model. This ultrametric structure in the long time dynamics can be obtained in the model here only by including terms to $`O(u^2)`$ in the dynamical equations – there is a direct analogy with the equilibrium solution of quantum rotors,  where RSB occurs when $`O(u^2)`$ terms are included in the equilibrium solutions. (The approach of Read, Sachdev, and Ye was slightly different from ours, since they expressed all terms in the action in terms of the Hubbard-Stratonovich field $`Q^{ab}`$, rather than working directly with the spin correlations, as we do here).

An important feature in the aging regime is the occurence of triangle relations between correlations at different time scales. These triangle relations have an ultrametric structure analagous to that found in RSB. At sufficiently large times $`t_1`$ and $`t_2`$, it is possible to express the correlation at intermediate times, $`t_2<t<t_1`$, in terms of a function $`f`$, which depends only on the correlations and has no explicit time dependence.  Mathematically

$$C(t_1,t_2)=f[C(t_1,t),C(t,t_2)],$$
(127)
and there is an inverse function $`\overline{f}`$

$$C(t_1,t)=\overline{f}[C(t_1,t_2),C(t_2,t)].$$
(128)
Cugliandolo and Kurchan  give a complete account of these triangle relations and the properties of the functions $`f`$ and $`\overline{f}`$. The function $`f`$ can have fixed points $`a`$, such that $`a=f(a,a)`$. Each of these fixed points constitutes a correlation scale. We make use of this approach to calculate the FDT violation factor $`X`$, in the long time dynamics of the quantum rotor model.

The saddle point equations are written down to $`O(u^2)`$ in Section III. To obtain the appropriate equations in the long time regime, the response must be split into a stationary part and an aging piece, as in Equations (114) and (116). At long times, the contributions to the dynamical equations from the bath kernels should be negligible, since the system has been in contact with the bath sufficiently long for one time quantitites to have reached a limit. What is studied here is how the two time quantities evolve after the interaction with the bath has ceased. We assume WEB and WLTM, and treat integrals in the manner explained by Cugliandolo and Lozano.  Hence the equations we wish to solve are (for $`t_1t_2`$)

$`0`$ $`=`$ $`{\displaystyle \frac{1}{2g}}{\displaystyle \frac{^2}{t_1^2}}R(t_1,t_2)+\lambda _1R(t_1,t_2)`$ (133)
$`+\lambda _2R(t_1,t_2)C(t_1,t_2)^2{\displaystyle \frac{1}{3}}\lambda _2\mathrm{}^2R(t_1,t_2)^3`$
$`+2J^2{\displaystyle _0^{\mathrm{}}}𝑑tR(t_1,t)R(t,t_2)`$
$`+\lambda _4{\displaystyle _0^{\mathrm{}}}𝑑tC(t_1,t)^2R(t_1,t)R(t,t_2)`$
$`{\displaystyle \frac{1}{3}}\lambda _4\mathrm{}^2{\displaystyle _0^{\mathrm{}}}𝑑tR(t_1,t)^3R(t,t_2),`$
and

$`0`$ $`=`$ $`{\displaystyle \frac{1}{2g}}{\displaystyle \frac{^2}{t_1^2}}C(t_1,t_2)+\lambda _1C(t_1,t_2)+\kappa _2R(t_1,t_2)`$ (141)
$`+{\displaystyle \frac{1}{3}}\lambda _2C(t_1,t_2)^3{\displaystyle \frac{1}{9}}\lambda _2C(t_1,t_2)R(t_1,t_2)^2`$
$`+\kappa _4C(t_1,t_2)^2R(t_1,t_2){\displaystyle \frac{1}{3}}\kappa _4\mathrm{}^2R(t_1,t_2)^3`$
$`+2J^2{\displaystyle _0^{\mathrm{}}}𝑑t\left[C(t_1,t)R(t_2,t)+R(t_1,t)C(t,t_2)\right]`$
$`+{\displaystyle \frac{1}{3}}\lambda _4{\displaystyle _0^{\mathrm{}}}𝑑tC(t_1,t)^3R(t,t_2)`$
$`+\lambda _4{\displaystyle _0^{\mathrm{}}}𝑑tC(t_1,t)^2R(t_1,t)C(t,t_2)`$
$`{\displaystyle \frac{1}{3}}\lambda _4\mathrm{}^2{\displaystyle _0^{\mathrm{}}}dt[3R(t_1,t)^2R(t_2,t)C(t_1,t)`$
$`+R(t_1,t)^3C(t,t_2)],`$
where we drop the aging subscript (since the only parts of the correlation and response we work with here are the aging pieces). The values for the coefficients are displayed in Appendix B.

The equations derived here are very similar to those that have been written down for the soft spin SK model.  If we assume that at sufficiently long times only terms that are invariant under time reparametrizations remain (more explanation is given in Section V D ), then the dynamical equations take the form

$`0`$ $`=`$ $`\lambda _1R(t_1,t_2)+\lambda _2C(t_1,t_2)^2R(t_1,t_2)`$ (144)
$`+2J^2{\displaystyle _0^{\mathrm{}}}𝑑tR(t_1,t)R(t,t_2)`$
$`+\lambda _4{\displaystyle _0^{\mathrm{}}}𝑑tC(t_1,t)^2R(t_1,t)R(t,t_2),`$
$`0`$ $`=`$ $`\lambda _1C(t_1,t_2)+{\displaystyle \frac{1}{3}}\lambda _2C(t_1,t_2)^3`$ (148)
$`+2J^2{\displaystyle _0^{\mathrm{}}}𝑑t\left[C(t_1,t)R(t_2,t)+R(t_1,t)C(t,t_2)\right]`$
$`+{\displaystyle \frac{1}{3}}\lambda _4{\displaystyle _0^{\mathrm{}}}𝑑tC(t_1,t)^3R(t_2,t)`$
$`+\lambda _4{\displaystyle _0^{\mathrm{}}}𝑑tC(t_1,t)^2R(t_1,t)C(t,t_2).`$
None of the terms with coefficients proportional to $`\mathrm{}^2`$ enter into these asymptotic equations, hence the dependence on quantum effects is only through the coefficients $`\lambda _1`$, $`\lambda _2`$, and $`\lambda _4`$. There are also classical terms (in the sense that they do not have a coefficient proportional to $`\mathrm{}^2`$) that are not reparametrization invariant.

The equations above have extra terms relative to the terms considered by Cugliandolo and Kurchan,  which are those with coeffcient $`\lambda _4`$ – we can recover their results when these terms are unimportant. The reason that we have these terms is that we include all terms of $`O(u^2)`$ before looking at the long time limit. Following Cugliandolo and Kurchan we can convert the equations into a manifestly time reparameterization invariant form by introducing functionals $`F[C]`$ and $`H[C]`$

$`F[C]`$ $`=`$ $`{\displaystyle _C^q}𝑑C^{}X[C^{}],`$ (149)
$`H[C]`$ $`=`$ $`{\displaystyle _C^q}𝑑C^{}C_{}^{}{}_{}{}^{2}X[C^{}],`$ (150)
and postulating a modified version of the FDT to relate the correlation and response

$`R(t_1,t_2)`$ $`=`$ $`\beta X[C(t_1,t_2)]{\displaystyle \frac{}{t_2}}C(t_1,t_2)\theta (t_1t_2),`$ (151)
$`=`$ $`\beta {\displaystyle \frac{}{t_2}}F[C(t_1,t_2)]\theta (t_1t_2).`$ (152)
The relation (151) is also invariant under time reparameterization. We follow a similar reasoning to Ref.  to show that within an ultrametric scale

$`X[a_1^{}]={\displaystyle \frac{\lambda _2a_1^{}}{\beta }}{\displaystyle \frac{(2J^2+\lambda _4q^2)^{\frac{1}{2}}}{(2J^2+\lambda _4a_{1}^{}{}_{}{}^{2})^{\frac{3}{2}}}}.`$ (153)
We also find that within an ultrametic scale $`X[C]=X[a_1^{}]`$, and that the scales have vanishing measure and there is thus a continous ultrametric solution at correlation scale $`a_1^{}`$, provided the following condition is satisfied

$`{\displaystyle \frac{2x_1F[a_1^{}]x_2\lambda _2a_{1}^{}{}_{}{}^{2}}{\lambda _2a_1^{}+\beta \lambda _4F[a_1^{}](2a_1^{}X[a_1^{}]F[a_1^{}])}}>0,`$ (154)
where

$`x_1`$ $`=`$ $`\beta (2J^2+\lambda _4a_{1}^{}{}_{}{}^{2}),`$ (155)
$`x_2`$ $`=`$ $`\lambda _1+2\lambda _4\beta {\displaystyle _{a_1^{}}^q}𝑑C^{}C^{}F[C^{}],`$ (156)
$`F[a_1^{}]`$ $`=`$ $`{\displaystyle \frac{\lambda _2}{\beta \lambda _4}}\left[1\sqrt{{\displaystyle \frac{2J^2+\lambda _4q^2}{2J^2+\lambda _4a_{1}^{}{}_{}{}^{2}}}}\right].`$ (157)
The results here reduce to those found earlier for the classical SK model  in the limit that $`\lambda _40`$. Hence the solution for the FDT violation factor $`X[C]`$ is

$`X[C]={\displaystyle \frac{\lambda _2C}{\beta }}{\displaystyle \frac{(2J^2+\lambda _4q^2)^{\frac{1}{2}}}{(2J^2+\lambda _4C^2)^{\frac{3}{2}}}}.`$ (158)
Note that if we define $`q`$ to be the value of the correlation for which $`X[C]=1`$, then this implies $`q=\beta /\lambda _2=\frac{2}{3}\beta /(u^2\chi _{\mathrm{}}).`$

### D Reparametrization symmetry

In deriving Equations (144) and (148) we assumed that the equations at long times are reparametrization invariant. As shown recently,  this assumption is justified, since at long times the dynamical equations governing the system flow to a “fixed point” of the reparametrization group at which the equations are invariant under time reparametrization transformations. The time reparametrizations are transformations of the form

$$t\stackrel{~}{t}=h(t),$$
(159)
where $`h(t)`$ is a differentiable function with $`dh/dt1`$ (so as to stretch time). Transforming time also leads to transformation of the correlation functions – for a two-time correlation function $`G(t_1,t_2)`$, we define a transformation $`G\stackrel{~}{G}`$ such that

$`\stackrel{~}{G}(t_1,t_2)=\left({\displaystyle \frac{h}{t_1}}\right)^{\mathrm{\Delta }_1^G}\left({\displaystyle \frac{h}{t_2}}\right)^{\mathrm{\Delta }_2^G}G[h(t_1),h(t_2)],`$ (160)
where $`\mathrm{\Delta }_{1,2}^G`$ are the scaling dimensions of the correlator $`G`$ under the rescaling of the time co-ordinates $`t_{1,2}`$. We term $`\mathrm{\Delta }_1^G`$ and $`\mathrm{\Delta }_2^G`$ the advanced and retarded scaling dimensions respectively. The “fixed point” dynamical equations are a set of equations which are invariant under an R$`p`$G transformation, i.e. if they are satisfied by $`G`$, then they are also satisfied by $`\stackrel{~}{G}`$. The idea of irrelevancy under R$`p`$G transformations, introduced in Ref. , where certain terms in the long time limit scale to progressively negligible perturbations about an R$`p`$G fixed point, is the means used to obtain the dynamical equations at long times.

## VI Discussion

We have studied spin glasses of quantum rotors from a purely dynamical perspective. In the dynamical approach, the phase transition between the paramagnetic and glassy phase can be identified by looking at the critical slowing down of the dynamics. Alternatively, we also identify the transition at the breakpoint where it is no longer possible to satisfy the QFDT relation between correlators and response functions in the solution of the equations of motion. We find that, if one insists on a TTI solution, it is necessary to include a singular ($`\delta `$ function) piece in the correlation to balance the fluctuation dissipation relation. The amplitude of this singular term is proportional to $`q`$, and this simple minded TTI solution is the analog of the usual replica symmetric equilibrium solution.

For the glassy phase, we study the non-equilibrium dynamics in the aging regime, where TTI is broken. We find that the relation between correlation and response for the quantum rotor model has the same character as in the classical case – specifically the OEFDR has the same form, but different coefficients from the classical case. We show that all of the terms in the dynamical equations that are only present in the quantum version of the model (with an explicit $`\mathrm{}`$ dependence) are not invariant under time reparametrizations, but instead they are R$`p`$G irrelevant and do not contribute in the long-time limit. The quantum terms, however, alter the short-time dynamics and consequently renormalize the coefficients of the classical (R$`p`$G invariant) terms in the long-time dynamical equations.

These findings help us understand rather more precisely how the behaviour of a spin glass system is modified by the introduction of quantum dynamics. Bhatt  has argued that the scalings at the spin glass transition should be the same as in classical models, due to the different timescales involved – $`\beta \mathrm{}`$ is the timescale for the quantum case (this corresponds to a frequency of $`\omega _q=8\times 10^{11}T\mathrm{Hz}`$, where $`T`$ is the temperature in Kelvin), which at finite temperature will be much shorter than other relevant time scales in the problem. Another way to argue this is to look at the QFDT, which in the low frequency (long time) limit corresponds to the classical FDT. However, the glassy systems we consider here are never at equilibrium, and hence the long time limit in the non-equilibrium system is less obvious. One suggestion is that the QFDT should be generalized in a manner similar to the generalization to an OEFDR that differs from the classical FDT by introducing an effective temperature $`\beta X`$ as the argument of the hyperbolic tangent.  The picture we discuss here and in recent previous work  is that at long times, due to reparametrization invariance of the dynamical equations, the dynamics become classical in nature (as we would have naively expected from equilibrium); however, the effective temperature is different to that obtained in the corresponding classical model, due to quantum effects renormalizing coefficients.

In essence, we find that in models where quantum dynamics is introduced in a model with trivial spin commutation relations such as the rotors (in contrast to $`SU(2)`$ spins, for example) quantum effects are only important in basically two aspects of the problem. The first is an equilibrium issue: the redefinition of the phase boundary due to the addition of quantum fluctuations, which further disfavors an ordered phase. The second has a non-equilibrium character: the renormalization of the classical terms in the aging dynamical equations, which translates into a renormalized effective temperature in the OEFDR. In this sense, this class of quantum spin glasses only correspond to “renormalized” classical systems. The situation for truly $`SU(2)`$ quantum spins, however, is not clear and deserves further work.

In addition to the quantum-classical connection that we partly address in this paper, there are also interesting issues connected to the time reparametrization invariance of the long time dynamics. The time reparametrization of the classical equations of motion appears to be a generic feature of classical spin glass models. The invariance in the SK model was noticed by several authors,  and we naturally encounter it in the rotor model as well. The form of the OEDFR seems to be a generic consequence of the retarded and advanced scaling dimensions of $`C,R`$,  which in turn may be fixed by the form of the FDT. In this sense, it would be interesting to discover whether it is possible to construct different R$`p`$G fixed points, with different scaling dimensions.

## VII ACKNOWLEDGEMENTS

We acknowledge the hospitality of the Institute for Advanced Study at Princeton (C. C), where this work was started, of Boston University (M. P. K), and of the University of Houston (J. Y.). Support was provided by the NSF Grant DMR-98-76208, and the Alfred P. Sloan Foundation (C. C).

## A TTI solutions for the response

One can attempt a solution for the response of the form $`R(\omega )=P(\omega )+iQ(\omega )`$, It is then possible to solve for $`P`$ and $`Q`$ and determine the quantum critical point, by writing $`x(\omega )=a(\omega )+ib(\omega )`$. The solution is

$`R(\omega )`$ $`=`$ $`{\displaystyle \frac{1}{4J^2}}(a+ib)\pm {\displaystyle \frac{1}{4J^2}}\sqrt{\left(a^2b^28J^2\right)+2iab},`$ (A1)
which can be separated into real and imaginary parts:

$`P(\omega )`$ $`=`$ $`{\displaystyle \frac{a}{4J^2}}\pm {\displaystyle \frac{1}{4J^2}}\left(\left(a^2b^28J^2\right)^2+4a^2b^2\right)^{\frac{1}{4}}`$ (A3)
$`\times \mathrm{cos}\left(\mathrm{tan}^1\left({\displaystyle \frac{2ab}{\sqrt{a^2b^28J^2}}}\right)\right),`$
$`Q(\omega )`$ $`=`$ $`{\displaystyle \frac{b}{4J^2}}\pm {\displaystyle \frac{1}{4J^2}}\left(\left(a^2b^28J^2\right)^2+4a^2b^2\right)^{\frac{1}{4}}`$ (A5)
$`\times \mathrm{sin}\left(\mathrm{tan}^1\left({\displaystyle \frac{2ab}{\sqrt{a^2b^28J^2}}}\right)\right).`$
We obtain the critical point when the square roots in the arguments of the sine and cosine vanish.

## B Coefficients for the aging equations

The coefficients that appear for the dynamical equations in the aging regime are summarized below:

$`\lambda _1`$ $`=`$ $`{\displaystyle \frac{1}{2}}m^2+u(1+M)q+2(1+M)u^2B_{\mathrm{}}+4J^2\chi _{\mathrm{}}`$ (B2)
$`+{\displaystyle \frac{3}{2}}(1+M)u^2\gamma _{\mathrm{}}^{21}{\displaystyle \frac{1}{2}}(1+M)u^2\mathrm{}^2\gamma _{\mathrm{}}^{03},`$
$`\lambda _2`$ $`=`$ $`{\displaystyle \frac{3}{2}}(1+M)u^2\chi _{\mathrm{}},`$ (B3)
$`\kappa _2`$ $`=`$ $`2J^2\gamma _{\mathrm{}}^{10},`$ (B4)
$`\lambda _4`$ $`=`$ $`{\displaystyle \frac{3}{2}}(1+M)u^2,`$ (B5)
$`\kappa _4`$ $`=`$ $`{\displaystyle \frac{3}{2}}(1+M)u^2\gamma _{\mathrm{}}^{10},`$ (B6)
and

$`\gamma _{\mathrm{}}^{mn}`$ $`=`$ $`\underset{t_1\mathrm{}}{lim}{\displaystyle _0^{t_1}}𝑑tC_{ST}(t_1t)^mR_{ST}(t_1t)^n,`$ (B7)
$`B_{\mathrm{}}`$ $`=`$ $`\gamma _{\mathrm{}}^{11}+q\chi _{\mathrm{}}+\underset{t_1\mathrm{}}{lim}{\displaystyle _0^{t_1}}𝑑tR_{AG}(t_1,t)C_{AG}(t_1,t).`$ (B8)