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# Direct Observation of Superheating and Supercooling of Vortex Matter using Neutron Diffraction

## Abstract

We report the first observation of a striking history dependence of the structure function of the vortex matter in the peak effect regime in a Nb single crystal by using small angle neutron scattering combined with in situ magnetic susceptibility measurements. Metastable phases of vortex matter, supercooled vortex liquid and superheated vortex solid, have been identified. We interpret our results as direct structural evidence for a first-order solid-liquid transition at the peak effect.
PACS numbers: 74.60.Ge, 61.12.Ex

A current subject of wide interest concerns the existence of a vortex solid-liquid transition in type-II superconductors . In addition to providing a model system for the study of melting and freezing, the vortex matter system offers unprecedented opportunities in studying the effects of quenched disorder on phase transitions. Recently, the magnetization jump in high-$`T_c`$ superconductors YBa2Cu3O7-δ (YBCO), a widely accepted thermodynamic signature of a vortex solid-liquid transition , and the peak effect, a well-known vortex-lattice softening anomaly in many low-$`T_c`$  and high-$`T_c`$  superconductors in which the critical current exhibits a peak rather than decreasing monotonically with increasing temperature, are found to occur at the same temperature . However, there is no direct structural evidence indicating whether the underlying phase transition is solid-to-solid, solid-to-liquid, or even liquid-to-liquid in origin. Since quenched disorder is known to have important consequences for phase transitions , whether a solid-liquid transition can occur when random pinning is effective has broad implications in condensed matter physics.

Small angle neutron scattering (SANS)  is presently the most powerful technique for probing the vortex structure in bulk superconductors. For high-$`T_c`$ superconductors, the magnetic penetration depth is typically quite long, yielding a very weak vortex signal in SANS experiments, which has so far prevented a direct structural study of the peak effect in high-$`T_c`$ systems. Recent effort has therefore focused on low-$`T_c`$ systems where one can detect the peak effect and measure the vortex structure using SANS in the same temperature and field regime , and for these purposes Nb is experimentally the most favorable system because of the short penetration depth and the availability of large, ultrahigh quality single crystals. However, it has been controversial as to whether there is a vortex solid-liquid transition in Nb and the two previous SANS studies of this issue were not conclusive . In the first study , a characteristic temperature at which the azimuthal width of the Bragg peaks starts to increase was interpreted as the vortex-lattice melting transition. In the second study , a nearly isotropic ring of scattering was observed in the peak-effect regime, but was interpreted as a disordered solid rather than a liquid. In both studies, only field-cooled vortex states were measured. We report here striking hysteresis in neutron diffraction patterns of the vortex state in the peak-effect regime of Nb. The metastability of supercooled and superheated vortex states is directly demonstrated by applying a weak perturbation and observing the evolution of the SANS patterns. These data provide direct evidence for a first-order vortex solid-liquid transition.

Our experiments were performed using the 30-m SANS instrument NG-7 at the NIST Center for Neutron Research. The increased flux on the SANS instrument due to a new liquid-hydrogen cold source turns out to be important, but the key improvement provided by the present experiment is that the SANS and the ac magnetic response of the vortex array are measured simultaneously in situ. Thus one can correlate the ordering in the vortex state directly with the macroscopic vortex dynamics. The coil for the magnetic ac susceptibility measurements can also be used to apply a small ac field to dynamically perturb the vortex system, allowing an in situ determination of the metastability of the vortex states.

The sample is a Nb single crystal of 99.998$`\%`$ purity, a cylinder with a slightly uneven diameter from 1.316 cm at one end to 1.169 cm at the other, and 2.48 cm in length. The incident neutron beam has a mean wavelength $`\lambda `$=6.0 Å and a bandwidth $`\mathrm{\Delta }\lambda `$/$`\lambda `$=0.11. The neutron beam traverses through the central region of the sample, defined by a cadmium mask (0.7 cm in diameter), along the cylindrical axis which coincides with the three-fold symmetric $`<`$111$`>`$ crystallographic direction. The dc magnetic field is applied by a horizontal superconducting magnet along the same direction. The absolute accuracy of the measured sample temperature is $`\pm `$ 0.20 K with a temperature stability better than $`\pm `$ 0.025 K.

The peak-effect regime of the Nb sample is determined in situ by measuring the characteristic dip in the temperature dependence of the real-part of the ac magnetic susceptibility $`\chi ^{}(T)`$, as shown in Fig.1(a) for $`H`$=3.75 kOe. The pronounced diamagnetic dip in $`\chi ^{}(T)`$ of the ac susceptibility corresponds to a strong peak effect in the critical current (or nonlinear conductance) in the sample . The onset, the peak, and the end of the peak effect are denoted by $`T_o(H)`$, $`T_p(H)`$, and $`T_{c2}(H)`$, respectively. (In YBCO, the end of the peak effect is still far below $`T_{c2}(H)`$.) Fig.1(b) shows the window of our experiment. The upper critical field $`H_{c2}`$(4.20K) = 4.23 kOe of this sample is higher than that of Ref. but similar to that of Ref.. The lower critical field line, separating the Abrikosov and Meissner phases, is estimated from the first appearance of vortex scattering in the SANS.

For each ($`T,H`$), we measure the vortex SANS patterns for different thermal paths. For low temperatures the vortex SANS images show sharp Bragg peaks with sixfold symmetry in agreement with previous studies , independent of the thermal history. An example is shown in the inset of Fig.1(b) for $`H`$=3.75 kOe and $`T`$=3.50 K. However, the vortex SANS pattern starts to show striking history dependence as the peak-effect regime is approached. For clarity, we define the field-cooled (FC) state as when the sample is cooled to the target temperature in a magnetic field, while the zero-field-cooled (ZFC) state is reached by cooling the sample in zero field to the target temperature and then increasing the magnetic field to the desired value. A field-cooled-warming (FC-W) state is when the system is cooled in field to a much lower temperature ($``$ 2 K) then warmed back to the final temperature.

For the FC path, the vortex SANS patterns show nearly isotropic rings for $`T_p<T<T_{c2}`$ and broad Bragg spots for $`T<T_p`$. There is no clear sharpening in the Bragg peaks when $`T_o`$ is crossed. Only at a lower $`T<T_p`$ do the Bragg peaks become sharp. In contrast, for the ZFC and the FC-W paths, the sharp Bragg spots are observed for all temperatures up to $`T_{c2}`$. Shown in the top panel of Fig.2 are the ZFC and FC images at $`H`$=3.75 kOe and $`T`$=4.40 K, which is just below $`T_o`$(3.75kOe)=4.50 K. The images in the mid panel are for $`H`$=4.00 kOe and $`T`$=4.40 K, which is 0.10 K above $`T_p`$(4.0kOe)=4.30 K. The intensities at the radial maximum for the mid panel SANS data are plotted in the lower panel. The sharp Bragg spots for the ZFC state indicate a vortex lattice with long-range-order (LRO) , while the broad spots for the FC state suggest a disordered phase with short-range-order.

The orientational order of the vortex assembly can be quantified by the azimuthal widths of the Bragg peaks at the radial position of the intensity maximum. The azimuthal widths $`\mathrm{\Delta }\theta `$ of the Bragg peaks can be obtained by fitting six Gaussian peaks to the data, for each ($`T,H`$) and path. Likewise, the translational order of the vortex assembly can be quantified by the radial widths $`\mathrm{\Delta }Q`$ of the Bragg peaks. The Gaussian widths are plotted in Fig.3. Clearly, the ZFC states are more ordered than the FC states, translationally and orientationally, across the peak-effect regime. To determine the positional correlation of the vortex lines along the field direction, the rocking curves (Bragg peak intensity vs. the relative angle between the neutron beam and the applied magnetic field) of the ZFC and FC states at $`H`$=3.75 kOe and $`T`$=4.40 K are also measured. The rocking-curve width for the FC state is 30$`\%`$ larger than that of the ZFC state, suggesting that the vortex lines are entangled  in the FC states, but nearly straight in the ZFC (and FC-W) states.

Since a simultaneous broadening in radial and azimuthal widths is characteristic of a liquid (or glass) , the hysteresis in both $`\mathrm{\Delta }\theta `$ and $`\mathrm{\Delta }Q`$ suggests a first-order vortex solid-liquid (or glass) transition. A controversial issue is the location of the underlying equilibrium phase transition in the vortex matter relative to the position of the peak effect . One interpretation  places the conjectured vortex solid-liquid transition $`T_m`$ at $`T_p`$, consistent with the recent experiments  in YBCO where the magnetization jump was found to coincide with the peak effect (the two are also related in other high-$`T_c`$ systems ). Another widely held view, is based on the classical Lindemann criterion which would place $`T_m`$ at $`T_{c2}(H)`$ for Nb, provided the vortex-lattice elastic moduli are well-behaved . In this scenario, the FC disordered phase seen here (as well as in ) is a supercooled liquid and the thermodynamic ground state is an ordered solid across the entire peak-effect regime. The third scenario places $`T_m`$ at or below the onset of the peak effect .

We find that it is possible to experimentally determine the ground state, and consequently the approximate position of $`T_m`$, of the vortex system. For this purpose, we use the ac susceptibility coil to apply a small ac magnetic field to shake the vortex assembly and use the SANS to observe how the structure of the system evolves. Even though the true ground state of the vortex system may not have been reached in the time scale of the shaking experiment due to random pinning, the evolution of the diffraction patterns leaves little doubt regarding the nature of the ground state.

As shown in Fig.4(a), after applying an ac field of 3.3 Oe at 100 Hz (1 kHz gives similar results) for $`10^3`$ sec, the ordered ZFC vortex lattice becomes completely disordered. Preliminary time-dependent data show that the Bragg peaks start to disappear within the first $`10^2`$ sec of the shaking experiment. In contrast, no measurable difference can be found for the disordered FC vortex states before and after the ac field is applied (for up to 104 sec). By using the same approach, we find that the FC disordered states for $`T<T_p`$ are metastable and the ordered ZFC state is the ground state, opposite to that for $`T>T_p`$. In the $`T<T_p`$ regime, the metastability is obviously stronger since a much larger ac field is needed to change the metastable state. We find that an ac field of 50 Oe (at $``$ 0.1 Hz, using the superconducting magnet at non-persistent mode) can crystallize the disordered FC states at $`T<T_p`$. The shaking effects of an ac magnetic field were also observed in transport  and ac magnetization  in the peak-effect region in 2H-NbSe2, and were interpreted as a structural re-organization in the vortex matter, consistent with our direct SANS observations here.

The metastable nature of the ZFC ordered state for $`T>T_p`$ can also be observed in a field ramping experiment. For example, at a field ramp (increase) rate of less than 5 Oe/sec, the final vortex state (at $`T>T_p`$) is always ordered. In contrast, a ramp rate larger than 40 Oe/sec always results in a disordered state. However, the field ramping experiment alone cannot rule out a trivial possibility that the sample was heated to above $`T_{c2}(H)`$ during the field ramping by the induced screening current. If this happens, after the field ramping stops, the sample cools back to the set temperature in field and the final state is actually a FC state. In the shaking experiment, the ac susceptibility of the sample is monitored and serves as an in situ thermometer to ensure that the sample temperature never fluctuates to above $`T_{c2}(H)`$ during the entire SANS run (1 hour).

Thus we conclude that, for $`T>T_p`$, the ordered ZFC vortex lattice is a superheated state and the ground state of the vortex system is a disordered vortex liquid, while for $`T<T_p`$, the ground state is a vortex crystal (or Bragg glass ), and the disordered FC state is a supercooled vortex liquid. A thermodynamic phase transition must have taken place in the region of the peak effect, $`T_mT_p`$. This is consistent with the observations in YBCO where the magnetization jump was found to coincide with the peak effect . In principle, one should also observe a discontinuous change of $`Q_o`$ when the vortex solid melts. Unfortunately, the expected shift in $`Q_o`$ due to the density change at the vortex solid-liquid transition is below our resolution limit, as we estimate here. From thermodynamic considerations , using the Clausius-Clapeyron relations, the vortex density change at $`T_m`$ is of the order $`\mathrm{\Delta }B=\frac{4\pi c_{L}^{}{}_{}{}^{2}C_{66}}{T_mdH_m/dT}`$ where $`c_L`$ is the Lindemann number and $`C_{66}\frac{B_{c2}^2}{4\pi }\frac{b(1b)^2}{8\kappa ^2}`$ is the vortex-lattice shear modulus, $`b=B/B_{c2}`$. For Nb at $`H`$=4.00 kOe, $`T_mT_p`$=4.30 K ($`T_{c2}`$=4.50 K), $`dH_m/dT`$= -0.846 kOe/K, and $`C_{66}`$$``$ 0.6x104 erg/cm3 assuming a reasonable $`\kappa `$1 and Lindemann number $`c_L`$=0.1, the upper bound for the jump $`\mathrm{\Delta }B`$ at melting is about 0.2 G. For a triangular lattice before melting $`Q_o(B=H)=2\pi \sqrt{\frac{2}{\sqrt{3}}}\sqrt{\frac{H}{\varphi _o}}`$, the expected $`\mathrm{\Delta }Q_o`$ $``$ 3x10$`{}_{}{}^{5}Q_{o}^{}`$ which is far too small to be resolved by the present SANS instruments. In Fig.4(b), the radial peak position $`Q_o`$ remains unchanged after shaking-induced melting, consistent with the above estimate.

Another interesting feature in Fig.3 is that there appears to be a characteristic temperature below which the vortex state is insensitive to its thermal history. For example, at $`H`$=3.75 kOe, the FC, ZFC, and FC-W states at 3.50 K are all ordered. The crossover temperature, $`t0.85`$ in Fig.3, is in fact very close to the melting line identified previously  (which was based on the measurements of the FC states). We interpret this temperature as the lower limit for supercooling.

A closer examination of the diffuse scattering rings in Figs.1$`\&`$2 suggests that they are not completely isotropic, indicating some short-range correlations. We attribute this short-range order to the coupling of the vortex liquid to the atomic crystal lattice, since experimentally one finds that in the Bragg solid phase, the specific orientation of the vortex lattice is always fixed to a certain crystallographic orientation of the sample. (This is the case for all low-$`T_c`$ and high-$`T_c`$ systems .) In the supercooled state (top-right in Fig. 2), the highly correlated vortex liquid , reminiscent of the hexatic liquid phase in 2D melting , is also likely related to this coupling.

We point out that our results imply the absence of superheating in conventional transport experiments with a large drive current. This solves a well-known puzzle  in which the history dependence of the nonlinear resistance always vanishes at $`T_p(H)`$. Only with extremely low drive currents may one observe the subtle effects of superheating in transport . The superheating of vortex solid contrasts sharply with that in regular bulk solids where surface melting prevents superheating . Surface melting of vortex solid is likely suppressed by the surface barrier in type-II superconductors.

In summary, we have observed a striking hysteresis in the SANS patterns of the vortex matter in the peak effect regime of a high quality Nb single crystal. The FC vortex states are disordered across the entire peak effect region and can be supercooled to below the onset of the peak effect. In contrast, the ZFC or the FC-W vortex states are ordered up to $`H_{c2}(T)`$. The ordered ZFC/FC-W vortex lattices near $`H_{c2}(T)`$ are identified as superheated solids which can be melted (disordered) by applying a small ac magnetic field. We interpret our SANS hysteresis data as direct evidence for a first-order vortex solid-liquid (glass) transition.

We thank C.J. Glinka for assistance and J.J. Rush for providing the Nb crystal; C. Elbaum, A. Houghton, J.M. Kosterlitz, H.J. Maris, and S.C. Ying for discussions. This work was supported in part by NSF through Grant No. DMR-0075838, the A.P. Sloan Foundation (XSL), and the Brown Salomon Award program.

Figure Captions:

Fig.1: Peak effect and the field-temperature ($`HT`$) phase diagram of Nb. (a) Representative ac magnetic susceptibility $`\chi ^{}(T)`$ vs. $`T`$ for $`H_{dc}`$=3.75 kOe (field-cooled). $`H_{ac}`$=3.3 Oe and $`f`$=1.0 kHz. $`H_{dc}||H_{ac}`$. (For details on ac magnetic measurements, see .) Inset: the global $`HT`$ phase diagram for the Nb crystal used in this study. (b) Expanded view of the $`HT`$ phase diagram for Nb (the shaded box in (a)). Two representative SANS images of the field-cooled vortex states are shown (no background subtraction).

Fig.2: History-dependent neutron diffraction patterns. $`T`$=4.40 K for all images. The SANS images of the ZFC and FC vortex states for $`H`$=3.75 kOe (top panel: below the onset of the peak effect) and $`H`$=4.00 kOe (mid panel: near the upper end of the peak-effect regime). The thick arrows indicate how the SANS images evolve after applying a small ac magnetic field (see text). The lower panel shows the intensity data at the radial maximum as a function of the azimuthal angle $`\theta `$ for the ZFC and FC SANS data (background subtracted) at $`H`$=4.00 kOe and $`T`$=4.40 K.

Fig.3: Temperature dependence of the SANS widths. (a) The azimuthal widths of the Bragg peaks at $`Q_o`$ and (b) the radial widths vs. reduced temperature for ZFC, FC, and FC-W vortex states. The FC-W data points at 3.75 kOe and 4.40 K are indicated by the crosses (and marked by arrows). The instrumental resolution in width is marked in (a). The lines are guides for the eye. The dashed lines indicate $`T_p(H)`$.

Fig.4: The effect of an ac field, $`H_{ac}`$=3.3 Oe and $`f`$=100.0 Hz, on the ordered ZFC state for $`H`$=4.00 kOe and $`T`$=4.40 K (above $`T_p(H)`$). (a) $`I(Q_o)`$ vs. azimuthal angle; (b) the intensity $`I(Q)`$ (averaged over the azimuthal angle) as a function of the momentum transfer $`Q`$. The location of the radial maximum $`Q_o`$ is found by fitting $`I(Q)`$ to a Gaussian. The lines are Gaussian fittings.


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# Out-of-equilibrium thermodynamic relations in systems with aging and slow relaxation

## I INTRODUCTION

Glassy systems like spin-glasses and structural glasses below the glass transition temperatures are out of equilibrium even on the macroscopic time scale. Thus, the slow dynamics of glassy systems has been a subject of continuous interest in the past years . Experimentally, the anomalous dynamical behaviors are characterized by slow relaxation with long time tail and aging phenomena.

Among them, aging phenomena are the most striking dynamical behaviors as follows: Two-time quantities like the correlation functions $`C(t,t^{})`$ explicitly depend on the time elapsed after the quench $`t^{}`$ (the waiting time). If the waiting time $`t^{}`$ is of microscopic time scale, the phenomena are merely transient on the way of relaxation to equilibrium. However, dependence on the waiting time continues even when $`t^{}`$ is so large that one-time quantities like the magnetization are asymptotically close to time-independent values . Since these phenomena mean that the dynamics is not stationary, aging is a sign showing that these systems are out of equilibrium even in macroscopic time scale, i.e. several days or weeks.

These aging phenomena appear also in mean-field models of spin-glasses and do not disappear even in the infinite waiting time limit . In addition, the phase space of these models decomposes into a large number of areas separated with infinitely high free energy barriers. Thus, glassy systems never reach true equilibrium and hence they are beyond the scope of thermodynamics and equilibrium statistical mechanics. Hence, in order to describe thermodynamic properties of glassy systems, out-of-equilibrium thermodynamics based on a dynamical description without the assumption of ergodicity is necessary.

In investigation of such anomalous dynamical behavior of glassy systems, it was found that aging phenomena have some universal properties. Theoretical analyses have suggested that there are two time regimes characterized by different dynamical properties of the two-time correlation function $`C(t,t^{})`$ and the associated linear response function $`R(t,t^{})`$ . In the first time regime where the time difference $`tt^{}`$ is short compared to $`t^{}`$, the dynamics looks stationary and the usual fluctuation-dissipation theorem (FDT) holds. On the other hand, in the second time regime where the time difference is comparable to $`t^{}`$, aging phenomena occur, i.e. $`C(t,t^{})`$ depends on $`t^{}`$ apart from dependence on $`tt^{}`$. In addition, it is known that the usual FDT between the correlation $`C(t,t^{})`$ and the response function $`R(t,t^{})`$ should be modified in a well-defined way which involves the rescaling of the temperature . The modification was found to be valid not only for mean-field models but also for other glassy systems: spin-glass models with finite-range interactions , real spin-glasses , structural glasses  and a model of phase separation . In addition, it is known for some glassy systems that the correlation function $`C(t,t^{})`$ obeys the scaling law that it depends on $`t`$ and $`t^{}`$ only through the value of $`\xi (t)/\xi (t^{})`$, where $`\xi (t)`$ is a system-dependent increasing function of time.

Aging of the correlation function and the modification of FDT imply that properties of the work done by modulating an external field in an isothermal process are completely different from properties predicted by traditional thermodynamics. In addition, the existence of the two time scales implies that thermodynamic properties must strongly depend on experimental time scales. Hence, the experimental time scale dependence of the thermodynamic properties of glassy systems should be investigated to construct out-of-equilibrium thermodynamics for glassy systems.

In order to describe our results precisely, we summarize thermodynamics for an isothermal process. Thermodynamics tells that when one quasistatically changes the external field the work needed for the change is independent of a path of changing the external field. In addition, the quasistatic work is equal to the change of the Helmholtz free energy. When the process is not quasistatic, the work is larger than the quasistatic work. This fact is called the principle of the minimum work and is derived from the second law of thermodynamics.

We show that the properties described above do not hold in systems with aging. More precisely, there are two experimental time regimes characterized by different thermal properties. The first regime is a time-domain where the waiting time is much longer than the time lapse of the process. We call the time lapse the measurement time. In this regime, the principle of the minimum work holds even though a system is out of equilibrium. More precisely, when the process is not infinitely slow, the work needed for the process is larger than the work for an infinitely slow process. In addition, value of the work for the infinitely slow process depends only on the initial state and the final state and hence it can play a role of a free energy.

The second regime is the experimental time regime where the length of the measurement time are comparable to that of the waiting time. In this regime, for the single-correlation-scale systems such as $`p`$-spin spherical spin-glasses the work done in an infinitely slow operation depends on the path of changing the field even when the waiting time is infinite. This property form a striking contrast to the consequence of traditional thermodynamics described above. On the other hand, for the multi-correlation-scale systems such as Sherrington-Kirkpatrick model, the work done in an infinitely slow operation is independent of the path.

In Sec. II, we describe an isothermal process considered in this paper and introduce the two time regimes which characterize the experimental time scales and play a significant role in this paper. In Sec. III, we see that in the first time regime, usual thermodynamic relations hold even though the system is out of equilibrium. The only difference is that the value of the work in an infinitely slow operation $`W_s`$ is different from that of the change of the free energy calculated from equilibrium statistical mechanics. In Sec. IV, we present general discussion on properties of the work $`W_s`$ in an infinitely slow operation in the second time regime and derive conditions when $`W_s`$ depends on the path of changing the external field. In Sec. V, by using the results obtained in the previous section, we show that for the single-correlation-scale systems the work in an infinitely slow operation depends on the path of changing the external field as a consequence of aging. Possibility of observation of this path-dependence is also discussed. In addition, we show that for the multi-correlation-scale systems $`W_s`$ is not path-dependent. Our results are summarized in Sec. VI, where implications of our results on thermodynamics of glassy systems and experimental protocols to observe quasiequilibrium properties are discussed.

## II An isothermal process and two time regimes

We describe an isothermal process to consider thermodynamic properties when aging occurs. A simple way to observe aging phenomena is through the following field cooling process (Fig. 1); The temperature of the heat bath is decreased in a small field $`H_0`$ to a sub-critical temperature at time 0. After a waiting time $`t_w`$ the field begins to change according to a given time-dependence $`H_0+H(t)`$. This change of the field continues for a period of $`\mathrm{}t`$. The initial and final values of $`H(t)`$ are $`H(t=t_w)=0`$ and $`H(t=t_w+\mathrm{}t)=\mathrm{}H`$. We refer to $`\mathrm{}t`$, the time lapse of the change of the field, as the measurement time. The waiting time $`t_w`$ and the measurement time $`\mathrm{}t`$ characterize the experimental time scales.

When the field is so weak that the response is linear, the work $`W`$ done on the sample during the process is given in terms of the response function $`R(t,t^{})`$ by

$$W=_{t_w}^{t_w+\mathrm{}t}𝑑t\frac{dH(t)}{dt}M(t),$$
(1)
where the “magnetization” $`M(t)`$ is given by

$$M(t)=_{\mathrm{}}^0𝑑t^{}R(t,t^{})H_0+_0^t𝑑t^{}R(t,t^{})H_0+_{t_w}^t𝑑t^{}R(t,t^{})H(t^{}).$$
(2)
Since we are interested in long waiting time behavior, the contribution of the first term of Eq. (2) is ignored. For feasibility of showing long time behavior, we rewrite Eq. (2) by integration by part to express $`M(t)`$ in terms of a susceptibility $`\chi (t,t^{})`$ instead of the response function;

$`W`$ $`=`$ $`H_0{\displaystyle _{t_w}^{t_w+\mathrm{}t}}𝑑t{\displaystyle \frac{dH(t)}{dt}}\chi (t,0)`$ (4)
$`{\displaystyle _{t_w}^{t_w+\mathrm{}t}}𝑑t{\displaystyle \frac{dH(t)}{dt}}{\displaystyle _{t_w}^t}𝑑t^{}{\displaystyle \frac{dH(t^{})}{dt^{}}}\chi (t,t^{}),`$
where the susceptibility is defined as

$$\chi (t,t^{})_t^{}^t𝑑t^{\prime \prime }R(t,t^{\prime \prime }).$$
(5)
In order to discuss the dependence of the work on the waiting time and the measurement time, we rewrite the expression of the work by the transformations: $`ts(tt_w)/\mathrm{}t`$, $`H(t)h(s)H(s\mathrm{}t+t_w)/\mathrm{}H`$. We assume that $`dh(s)/ds`$ and $`d^2h(s)/ds^2`$ are finite, in order to exclude the unrealistic cases where the speed and the acceleration of changing the field is infinity. For example, the path such as $`h(s)=\sqrt{s}`$ is excluded, since $`dh(s)/ds`$ and $`d^2h(s)/ds^2`$ are infinite at $`s=0`$.

Thus, the work is reduced to

$`W/(\mathrm{}H)^2=H_0/\mathrm{}H{\displaystyle _0^1}𝑑s{\displaystyle \frac{dh(s)}{ds}}\chi (s\mathrm{}t+t_w,0)`$ (6)
$`{\displaystyle _0^1}𝑑s_1{\displaystyle \frac{dh(s_1)}{ds_1}}{\displaystyle _0^{s_1}}𝑑s_2{\displaystyle \frac{dh(s_2)}{ds_2}}`$ (7)
$`\times \chi (s_1\mathrm{}t+t_w,s_2\mathrm{}t+t_w),`$ (8)
which implies that the dependence of the work on the experimental time scales is determined by that of the susceptibility. Since the first term of Eq. (8) becomes a constant $`H_0\chi (\mathrm{},0)/\mathrm{}H`$ in the long waiting time limit which we are interested in, we will analyze properties of the second term of Eq. (8), i.e. the work done in the zero-field cooling process ($`H_0=0`$), in the rest of this chapter for simplicity;

$$W/(\mathrm{}H)^2=_0^1𝑑s_1\frac{dh(s_1)}{ds_1}_0^{s_1}𝑑s_2\frac{dh(s_2)}{ds_2}\chi (s_1\mathrm{}t+t_w,s_2\mathrm{}t+t_w).$$
(9)
In order to discuss behavior of the susceptibility when aging occurs, we recapitulate the long-time behavior of the response function referred to in the previous section. It is known that there are two time regimes characterized by different behavior of the correlation function $`C(t,t^{})`$ and the FDT ;

* At long times $`t`$ and $`t^{}`$ such that $`tt^{}t^{}`$, the correlation function is the function of only the time difference $`tt^{}`$, i.e. the time-translational invariance (TTI) holds. In addition, although the sample is out of equilibrium, the usual FDT holds  as

$$R(tt^{})=\frac{1}{k_BT}\frac{C(tt^{})}{t^{}},$$
(10)
where $`C(\tau )`$ is defined as $`lim_t\mathrm{}C(\tau +t,t)`$. Since the properties of two-time quantities in this time regime are the same as that in equilibrium, this time regime is called the quasiequilibrium regime.
* Whereas, at long and well-separated times such that $`tt^{}t^{}`$, aging occurs, i.e. the two-time correlation function $`C(t,t^{})`$ depends on $`t^{}`$ even in the long time limit $`t^{}\mathrm{}`$. This implies no TTI and this time regime is called the aging regime. In addition, it is known that in the aging regime the FDT is modified as

$$R(t,t^{})=\frac{X[C(t,t^{})]}{k_BT}\frac{C(t,t^{})}{t^{}},$$
(11)
where the FDT violation factor $`X`$ is a function which depends on $`t,t^{}`$ only through the dependence of the correlation function $`C(t,t^{})`$ . Thus, a system cannot be considered to be in a quasiequilibrium state, since the usual FDT is strongly violated. When only one correlation scale exists apart from the quasiequilibrium regime, it is known that the FDT violation factor is a constant.

In order to clarify the meaning of the time region of the aging regime ($`tt^{}t^{}`$), we give an explicit expression of aging of the correlation function as

$$\underset{\genfrac{}{}{0pt}{}{\tau \mathrm{}}{\mu =t^{}/g(\tau )}}{lim}C(\tau +t^{},t^{})=\underset{\tau \mathrm{}}{lim}C[\tau +\mu g(\tau ),\mu g(\tau )]\widehat{C}(\mu ),$$
(12)
where $`g(t)`$ is a system-dependent function which characterizes the aging regime and $`\tau `$ is the time difference $`tt^{}`$. The correlation function $`\widehat{C}(\mu )`$ depends on the waiting time $`t^{}`$ through the value of $`\mu `$. Occurrence of aging means that the limiting function $`\widehat{C}(\mu )`$ takes a non-trivial value such that $`0<\widehat{C}(\mu )<q`$. Here, $`q`$ is the dynamical E-A order parameter. Thus, the time region of the aging regime is the time region where $`t^{}/g(tt^{})`$ is finite. Here, we assume that $`\mu `$ and $`g(\tau )`$ are positive.

This definition of aging is illustrated in terms of contour plot of the correlation function on $`\tau t^{}`$ plain (Fig. 2 (a)). The plot when aging occurs is completely different from that when aging does not occur (Fig. 2 (b)). The contour lines give the system dependent function $`g(t)`$ which characterizes the aging regime, since the contour lines are given by $`\mu =t^{}/g(\tau )`$ in the contour plot.

We show two examples of the function $`g(t)`$ and the aging regime for systems like spherical spin-glasses and real spin-glasses. In these systems, it is known that the correlation function behaves as a function of $`\xi (t)/\xi (t^{})`$, where the scaling function $`\xi (t)`$ is a system-dependent function . The function $`g(t)`$ is given in terms of $`\xi (t)`$ as $`g^1(t)=\xi ^1[r\xi (t)]t`$, where $`r`$ is a constant larger than unity. The inverse function of $`\xi (t)`$ exists since $`\xi (t)`$ is a monotonically increasing function. For example,

1. When $`\xi (t)=t`$,

$$\underset{\genfrac{}{}{0pt}{}{\tau \mathrm{}}{\mu =t^{}/\tau }}{lim}\frac{\xi (\tau +t^{})}{\xi (t^{})}=\underset{\genfrac{}{}{0pt}{}{\tau \mathrm{}}{\mu =t^{}/\tau }}{lim}\frac{\tau +t^{}}{t^{}}=\underset{\tau \mathrm{}}{lim}\frac{\tau +\mu \tau }{\mu \tau }=\frac{1+\mu }{\mu }.$$
(13)
Thus, $`lim_{\genfrac{}{}{0pt}{}{\tau \mathrm{}}{\mu =t^{}/\tau }}C(\tau +t^{},t^{})`$ is a function of $`\mu `$ and hence the aging regime is the time regime where $`t^{}/\tau `$ is finite.
2. When $`\xi (t)=\mathrm{exp}[(t/\tau _0)^{1\alpha }/(1\alpha )](0<\alpha <1)`$,

$$\underset{\genfrac{}{}{0pt}{}{\tau \mathrm{}}{\mu =t^{}/\tau ^{1/\alpha }}}{lim}\frac{\xi (\tau +t^{})}{\xi (t^{})}=\mathrm{exp}(\tau _0^{\alpha 1}\mu ^\alpha ).$$
(14)
Thus, $`lim_{\genfrac{}{}{0pt}{}{\tau \mathrm{}}{\mu =t^{}/\tau ^{1/\alpha }}}C(\tau +t^{},t^{})`$ is a function of $`\mu `$ and hence the aging regime is the time regime when $`t^{}/\tau ^{1/\alpha }`$ is finite.

From these results, it is shown by the definition of the susceptibility Eq. (5) that the behavior of the susceptibility depends on the time regimes according to the dependence of the behavior of the response function. In the quasiequilibrium regime, the susceptibility depends only on the time difference $`\tau tt^{}`$ and is given by the correlation function as

$$\chi (\tau )=\frac{1}{k_BT}[C(\tau )C(0)]$$
(15)
where $`C(\tau )lim_t^{}\mathrm{}C(\tau +t^{},t^{})`$. Whereas, in the aging regime, time translational invariance (TTI) does not hold and the susceptibility is given by the correlation function as

$$\chi (t,t^{})=\frac{1}{k_BT}_{C(t,t^{})}^{C(t,t)}𝑑CX(C)$$
(16)
where $`X`$ is the FDT violation factor defined by Eq. (11). It implies that the susceptibility is a function of the correlation function.

Since the difference of the two arguments of the susceptibility in Eq. (9) is $`(s_1s_2)\mathrm{}t`$, there are also two time regimes characterized by different dependence of the work on the experimental time scales $`\mathrm{}t`$ and $`t_w`$.

* When the waiting time is much longer than the measurement time ($`\mathrm{}tt_w`$), the susceptibility which appears in Eq. (9) obeys Eq. (15) since $`(s_1s_2)\mathrm{}ts_2\mathrm{}t+t_w`$ holds. Hence, from Eqs. (9) and (15) the work in this regime is written as

$`W/(\mathrm{}H)^2`$ $`=`$ $`{\displaystyle \frac{C(0)}{2k_BT}}+{\displaystyle \frac{1}{k_BT}}{\displaystyle _0^1}𝑑s_1{\displaystyle \frac{dh(s_1)}{ds_1}}`$ (18)
$`\times {\displaystyle _0^{s_1}}ds_2{\displaystyle \frac{dh(s_2)}{ds_2}}C[(s_1s_2)\mathrm{}t].`$
In the derivation,

$$_0^1𝑑s_1\frac{dh(s_1)}{ds_1}_0^{s_1}𝑑s_2\frac{dh(s_2)}{ds_2}=1/2$$
(19)
for any path $`h(s)`$ is used.
* On the other hand, when both the waiting time and the measurement time are long ($`\mathrm{}tt_w`$), the susceptibility obeys Eq. (16) since $`(s_1s_2)\mathrm{}ts_2\mathrm{}t+t_w`$ holds . In this regime, it is seen from Eq. (16) that the work is a functional of the correlation function which shows aging. The ambiguous relation $`t_w\mathrm{}t`$ is described explicitly in Sec. IV with the function $`g(t)`$ defined in Eq. (12).

We refer to the former case as the quasiequilibrium regime and the latter case as the aging regime without any confusion with the time regimes characterized by the behavior of the correlation and the response function.

## III the work in the quasiequilibrium regime

In this section, we investigate the properties of the work done on the sample when the measurement time $`\mathrm{}t`$ is short compared to the long waiting time $`t_w`$ (the quasiequilibrium regime).

### A The work done in an slow process

First, we derive the work done in an slow operation such that the measurement time $`\mathrm{}t`$ is so long that the correlation function relax to a time-independent value. This process is formulated by taking the infinite measurement time limit $`\mathrm{}t\mathrm{}`$. Glassy systems are out of equilibrium even in such an infinitely slow process. Hence, we call a process where the external field is changed infinitely slowly a “slow process” instead of a “quasistatic process”.

Since for the slow process the time lapse of the process is infinity, the work done in the slow process in the quasiequilibrium regime is given by taking the limit $`\mathrm{}t\mathrm{}`$ after taking the infinite waiting time limit of Eq. (18). Since the integrand, the correlation function, is finite, the order of limit and integration can be changed. Thus, we can write the work $`W_s`$ for the slow process as

$`W_s/(\mathrm{}H)^2`$ $`=`$ $`\underset{\mathrm{}t\mathrm{}}{lim}\underset{t_w\mathrm{}}{lim}W/(\mathrm{}H)^2`$ (20)
$`=`$ $`{\displaystyle \frac{C(0)}{2k_BT}}+{\displaystyle \frac{1}{k_BT}}{\displaystyle _0^1}𝑑s_1{\displaystyle \frac{dh(s_1)}{ds_1}}`$ (22)
$`\times {\displaystyle _0^{s_1}}ds_2{\displaystyle \frac{dh(s_2)}{ds_2}}\underset{\mathrm{}t\mathrm{}}{lim}C[(s_1s_2)\mathrm{}t].`$
Here, in order to give the expression of the work $`W_s`$, we introduce the dynamical Edwards-Anderson (E-A) order parameter defined as

$$q\underset{\tau \mathrm{}}{lim}\underset{t_w\mathrm{}}{lim}C(\tau +t_w,t_w).$$
(23)
Using Eq. (19) and the above definition, the work $`W_s`$ for the slow process is given by

$$W_s=\frac{(\mathrm{}H)^2}{2k_BT}[C(0)q].$$
(24)
Therefore, the work for the slow process in the quasiequilibrium regime is the difference of a state function, since the right hand side of Eq. (24) is independent of the path of changing the field $`h(s)`$ and dependent only on the thermodynamic variables ($`\mathrm{}H`$ and $`T`$) and constants intrinsic to the system ($`C(0)`$ and $`q`$). It is important to note that this property is derived by using only the FDT.

On the other hand, for usual systems apart from glassy systems, one may expect that equilibrium is usually achieved when $`t_w`$ is long ($`t_w\mathrm{}`$). So, thermodynamics can be applied and the work for the slow process is equal to the change of the Helmholtz free energy, $`\mathrm{}F_{eq}`$, calculated by equilibrium statistical mechanics. However, we show below that this naive expectation fails for glassy systems. More precisely, the work for the slow process, Eq. (24), is different from the change of the Helmholtz free energy calculated by equilibrium statistical mechanics. It is because the glassy systems are out of equilibrium even when the waiting time is infinite.

Assuming that $`A(t)`$ is a physical quantity coupled to the external field $`H(t)`$ linearly, we see from statistical mechanics with the assumption of ergodicity that the isothermal susceptibility $`\chi _T`$ is given by

$$\chi _T=\frac{1}{k_BT}A^2_{eq}A_{eq}^2_J$$
(25)
where $`\mathrm{}_{eq}`$ denotes average over the Gibbs-Boltzmann distribution and $`\mathrm{}_J`$ denotes disorder-average. Thus, the free energy difference $`\mathrm{}F_{eq}`$ due to change $`\mathrm{}H`$ of the external field is

$$\mathrm{}F_{eq}=\frac{(\mathrm{}H)^2}{2k_BT}A^2_{eq}A_{eq}^2_J$$
(26)
where $`A_{eq}^2_J`$ is the usual E-A order parameter. Since ergodicity is broken for glassy systems, the phase space decomposes into many pure states. Assuming that $`\mathrm{}_a`$ denotes the thermal average in local equilibrium in the pure state $`a`$ and $`F_a`$ denotes the free energy at the pure state $`a`$, we see that

$`A^2_{eq}={\displaystyle \underset{a}{}}P_a^{eq}A^2_a,`$ (27)
$`A_{eq}^2=({\displaystyle \underset{a}{}}P_a^{eq}A_a)^2.`$ (28)
where $`P_a^{eq}`$ is the probability that the system is found at the pure state $`a`$ in true equilibrium and is given by $`P_a^{eq}\mathrm{exp}(\beta F_a)/Z`$.

In order to compare $`W_s`$, Eq. (24), with $`\mathrm{}F_{eq}`$, Eq. (26), we rewrite Eq. (24) in terms of pure states. Since the correlation function is given by $`C(t,t^{})=A(t)A(t^{})_J`$ and the local equilibrium in pure states is achieved in the long time limit,

$`C(0)\underset{t^{}\mathrm{}}{lim}A(t^{})^2_J={\displaystyle \underset{a}{}}P_a^{ini}A^2_a_J,`$ (29)
$`q\underset{\tau \mathrm{}}{lim}\underset{t^{}\mathrm{}}{lim}A(\tau +t^{})A(t^{})_J={\displaystyle \underset{a}{}}P_a^{ini}A_a^2_J`$ (30)
where $`P_a^{ini}`$ is the probability that the system is found in pure state $`a`$ at time $`0`$. Since the system is out of equilibrium at time $`0`$, $`P_a^{eq}P_a^{ini}`$. Thus, $`A^2_{eq}_J`$ is not equal to $`C(0)`$. In addition, from Eqs. (28) and (30), $`A_{eq}^2_J`$ is not equal to $`q`$. Consequently, we conclude that the work $`W_s`$ for the slow process does not coincide with the free energy difference calculated by statistical mechanics with assumption of ergodicity.

### B The work when the measurement time is finite

We discuss the properties of the work when the measurement time is finite. From Eqs. (18) and (24), the difference between the work when the process is not slow and the work for the slow process is given by

$$WW_s=\frac{(\mathrm{}H)^2}{k_BT}_0^1𝑑s_1\frac{dh(s_1)}{ds_1}_0^{s_1}𝑑s_2\frac{dh(s_2)}{ds_2}\{C[(s_1s_2)\mathrm{}t]q\}.$$
(31)
$`C[(s_1s_2)\mathrm{}t]>q`$ when $`\mathrm{}t`$ is finite, since the quasiequilibrium regime is considered. Hence, the difference from the work for the slow process is positive for any path of changing the field, when the measurement time is finite. This implies the principle of minimum work;

$$WW_s,$$
(32)
where the equality holds only when the measurement time is infinite, i.e. the slow-process limit.

Our result is very similar to the consequence of thermodynamics which tells the work for non-quasistatic process is larger than the change of the Helmholtz free energy. However, our result is different from that and beyond the scope of thermodynamics since in our discussion the initial state and the final state of the process are out of equilibrium and the value of the work for the slow process is different from the value of change in the Helmholtz free energy derived by equilibrium statistical mechanics.

### C Long measurement time behavior of $`WW_s`$

The long measurement time behavior of $`WW_s`$ is analyzed in this subsection. We show that the behavior of $`WW_s`$ when the measurement time $`\mathrm{}t`$ is long but finite is determined by the long time behavior of the correlation function. We describe below the results for four types of behavior of the correlation function which include almost all types of relaxation of the correlation, e.g., the exponential, the power law , the logarithmic  and the stretched exponential relaxation . The derivations are given in Appendix A.

1. When the correlation function behaves as $`lim_\tau \mathrm{}\tau [C(\tau )q]=0`$, the difference is given by

$$WW_s\frac{(\mathrm{}H)^2}{k_BT}K_{\mathrm{}}_0^1𝑑s\left|\frac{dh(s)}{ds}\right|^2\frac{1}{\mathrm{}t},$$
(33)
where

$$K_{\mathrm{}}_0^{\mathrm{}}𝑑\tau [C(\tau )q]$$
(34)
and $`W_s`$ denotes the work for the slow process. This case includes the power law relaxation such that $`C(\tau )q+c\tau ^\alpha `$ when $`\alpha >1`$ and the stretched exponential relaxation ($`\mathrm{exp}(a\tau ^n),0<n<1`$) as well as the exponential relaxation .
2. When the correlation function behaves as $`lim_\tau \mathrm{}\tau [C(\tau )q]=c`$, the difference is given by

$$WW_s\frac{(\mathrm{}H)^2}{k_BT}c_0^1𝑑s\left|\frac{dh(s)}{ds}\right|^2\frac{\mathrm{ln}(\mathrm{}t)}{\mathrm{}t}.$$
(35)
These two results show that $`WW_s`$ is proportional to the inverse of the measurement time only when $`lim_\tau \mathrm{}\tau [C(\tau )q]=0`$. In these two cases, the difference from the work for the slow process takes the minimum value when the field increases linearly as $`h(s)=s`$, since we assume that $`dh(s)/ds`$ and $`d^2h(s)/ds^2`$ is finite.
3. When the correlation function obeys the power law relaxation, such that $`C(\tau )q+c\tau ^\alpha `$ ($`0<\alpha <1`$), the difference is given by

$`WW_s`$ $``$ $`{\displaystyle \frac{(\mathrm{}H)^2}{k_BT}}c{\displaystyle _0^1}𝑑s_1{\displaystyle \frac{dh(s_1)}{ds_1}}`$ (37)
$`\times {\displaystyle _0^{s_1}}ds_2{\displaystyle \frac{dh(s_2)}{ds_2}}{\displaystyle \frac{1}{(s_1s_2)^\alpha }}{\displaystyle \frac{1}{(\mathrm{}t)^\alpha }}.`$
In this case, the difference from $`W_s`$ obeys the power law whose exponent is equal to the exponent of the correlation function.
4. When the correlation function obeys the logarithmic relaxation $`C(\tau )q+c/\mathrm{ln}(\tau )`$, the difference also obeys the logarithmic relaxation as

$$WW_{qs}=\frac{(\mathrm{}H)^2}{2k_BT}\frac{c}{\mathrm{ln}(\mathrm{}t)}+O[\frac{\mathrm{ln}(\mathrm{ln}\mathrm{}t)}{(\mathrm{ln}\mathrm{}t)^2}].$$
(38)
In this case, the difference does not depend on the path $`h(s)`$.

Experimentally, these results tell how long the measurement should take and the suitable path of changing the external field in order to determine the value of the work for the slow process, i.e. the difference of a state function in quasiequilibrium regime.

## IV The work in the aging regime; general results

In this section, we discuss the properties of the work in the isothermal slow process when both the waiting time and the measurement time are long, i.e. in the aging regime, by using the modified FDT and aging of the correlation function introduced in Eqs. (11) and (12). Condition when the work for the slow process depends on the path changing the external field is obtained. By using the results obtained in this section, the path-dependence of the work for particular systems is discussed in the next section, Sec. V.

### A Path-dependence of the work for the slow process

As shown in Sec. II, in the aging regime the work is a functional of the correlation function which shows aging. The slow process of the aging regime is given by taking the long measurement time limit $`\mathrm{}t\mathrm{}`$ with holding the relation $`t_w\mathrm{}t`$, which guarantees that the slow-process limit is taken within the aging regime. The slow-process limit has always this meaning in this section.

The order of the slow-process limit and the integration can be changed since the susceptibility $`\chi `$ is finite. From Eq. (9) the work $`W_s`$ for the slow process in the aging regime is given by

$`W_s/(\mathrm{}H)^2`$ $`=`$ $`{\displaystyle _0^1}𝑑s_1{\displaystyle \frac{dh(s_1)}{ds_1}}{\displaystyle _0^{s_1}}𝑑s_2{\displaystyle \frac{dh(s_2)}{ds_2}}`$ (40)
$`\times \chi [\underset{\genfrac{}{}{0pt}{}{\mathrm{}t\mathrm{}}{t_w\mathrm{}t}}{lim}C(s_1\mathrm{}t+t_w,s_2\mathrm{}t+t_w)].`$
Thus, the dependence of $`lim_{\genfrac{}{}{0pt}{}{\mathrm{}t\mathrm{}}{t_w\mathrm{}t}}C(s_1\mathrm{}t+t_w,s_2\mathrm{}t+t_w)`$ on $`s_1`$ and $`s_2`$ determines the dependence of the work for the slow process on the path of changing the field $`h(s)`$; $`W_s`$ is independent of $`h(s)`$ if $`lim_{\genfrac{}{}{0pt}{}{\mathrm{}t\mathrm{}}{t_w\mathrm{}t}}C(s_1\mathrm{}t+t_w,s_2\mathrm{}t+t_w)`$ does not depend on $`s_1`$ and $`s_2`$. On the other hand, $`W_s`$ is a functional of $`h(s)`$ if $`lim_{\genfrac{}{}{0pt}{}{\mathrm{}t\mathrm{}}{t_w\mathrm{}t}}C(s_1\mathrm{}t+t_w,s_2\mathrm{}t+t_w)`$ depends on $`s_1`$ and $`s_2`$. We derive conditions when $`W_s`$ depends on $`h(s)`$ in the rest of this section.

In order to analyze $`lim_{\genfrac{}{}{0pt}{}{\mathrm{}t\mathrm{}}{t_w\mathrm{}t}}C(s_1\mathrm{}t+t_w,s_2\mathrm{}t+t_w)`$, we clarify the meaning of $`t_w\mathrm{}t`$ or the aging regime by using $`g(\tau )`$ in Eq. (12). By substitution $`t^{}s_2\mathrm{}t+t_w,\tau (s_1s_2)\mathrm{}t`$ in Eq. (12), we see that the following equation holds in the region except for the point $`s_1=s_2`$ which does not contribute to the value of the work by itself;

$$\underset{\genfrac{}{}{0pt}{}{\mathrm{}t\mathrm{}}{\mu =\frac{s_2\mathrm{}t+t_w}{g[(s_1s_2)\mathrm{}t]}}}{lim}C(s_1\mathrm{}t+t_w,s_2\mathrm{}t+t_w)=\widehat{C}(\mu ).$$
(41)
This equation implies that the aging regime is the experimental time regime where $`(s_2\mathrm{}t+t_w)/g[(s_1s_2)\mathrm{}t]`$ is finite and the slow-process limit of the correlation function in the integrand in Eq. (40) is a function of $`lim_{\genfrac{}{}{0pt}{}{\mathrm{}t\mathrm{}}{t_w\mathrm{}t}}(s_2\mathrm{}t+t_w)/g[(s_1s_2)\mathrm{}t]`$.

We discuss below the aging regimes and dependence of $`lim_{\genfrac{}{}{0pt}{}{\mathrm{}t\mathrm{}}{t_w\mathrm{}t}}C(s_1\mathrm{}t+t_w,s_2\mathrm{}t+t_w)`$ on $`s_1`$ and $`s_2`$ in four cases of the different long-time behaviors of $`g(t)`$ which exhaust all possibilities (see Fig. 3).

1. When $`lim_\tau \mathrm{}\tau /g(\tau )=\mathrm{}`$, $`t^{}/g(tt^{})`$ is finite only in the region $`t^{}tt^{}`$. In the region of integration of Eq. (40) except for the point $`s_2=0`$,

$$(s_2\mathrm{}t+t_w)/g[(s_1s_2)\mathrm{}t]\mathrm{}$$
(42)
as $`\mathrm{}t\mathrm{}`$ since $`t_w>0`$. An example of such $`g(\tau )`$ is $`g(\tau )=\mathrm{log}\tau `$. When $`g(\tau )=\mathrm{log}\tau `$ and $`s_20`$, $`lim_\mathrm{}t\mathrm{}(s_2\mathrm{}t+t_w)/g[(s_1s_2)\mathrm{}t]=\mathrm{}`$ as shown in Eq. (42). Since the point $`s_2=0`$ does not contribute to the value of the work by itself, the experimental time regime where $`(s_2\mathrm{}t+t_w)/g[(s_1s_2)\mathrm{}t]`$ is finite does not exist in this case. If there is no other aging regime except for that characterized by such $`g(\tau )`$ exists, only the quasiequilibrium regime contributes to the value of the work and hence the work for the slow process is independent of $`h(s)`$ and is given by Eq. (24).
2. When $`g(\tau )=\tau `$,

$$\frac{s_2\mathrm{}t+t_w}{g[(s_1s_2)\mathrm{}t]}=\frac{s_2\mathrm{}t+t_w}{(s_1s_2)\mathrm{}t}=\frac{s_2+t_w/\mathrm{}t}{s_1s_2}.$$
(43)
Thus, from Eq. (41), $`lim_{\genfrac{}{}{0pt}{}{\mathrm{}t\mathrm{}}{\mu ^{}=t_w/\mathrm{}t}}C(s_1\mathrm{}t+t_w,s_2\mathrm{}t+t_w)`$ is a function of $`(s_2+\mu ^{})/(s_1s_2)`$;

$`\underset{\genfrac{}{}{0pt}{}{\mathrm{}t\mathrm{}}{\mu ^{}=t_w/\mathrm{}t}}{lim}C(s_1\mathrm{}t+t_w,s_2\mathrm{}t+t_w)`$ (44)
$`=`$ $`\underset{\genfrac{}{}{0pt}{}{\mathrm{}t\mathrm{}}{\frac{s_2+\mu ^{}}{s_1s_2}=\frac{s_2\mathrm{}t+t_w}{g[(s_1s_2)\mathrm{}t]}}}{lim}C(s_1\mathrm{}t+t_w,s_2\mathrm{}t+t_w)`$ (45)
$`=`$ $`\widehat{C}({\displaystyle \frac{s_2+\mu ^{}}{s_1s_2}}).`$ (46)
It implies that the aging regime is the region where $`t_w/\mathrm{}t`$ is finite. In this aging regime the slow-process limit of the correlation function in the integrand of Eq. (40) depends on $`s_1`$ and $`s_2`$ if $`f(\mu )`$ in Eq. (41) is not a constant. It means that the work for the slow process, $`W_s`$, depends on the path of change of the external field, $`h(s)`$.
3. When $`lim_\tau \mathrm{}\tau /g(\tau )=0`$ and $`lim_\tau \mathrm{}g(\tau )/g(s\tau )g_r(s)(s<1)`$ exists,

$`{\displaystyle \frac{s_2\mathrm{}t+t_w}{g[(s_1s_2)\mathrm{}t]}}={\displaystyle \frac{s_2\mathrm{}t+t_w}{g(\mathrm{}t)}}{\displaystyle \frac{g(\mathrm{}t)}{g[(s_1s_2)\mathrm{}t]}}`$ (47)
$`{\displaystyle \frac{t_w}{g(\mathrm{}t)}}g_r(s_1s_2),`$ (48)
as $`\mathrm{}t\mathrm{}`$. An example of such $`g(\tau )`$ is $`g(\tau )=\tau ^\alpha (\alpha >1)`$. When $`g(\tau )=\tau ^\alpha (\alpha >1)`$, Eq. (48) holds;

$$\frac{s_2\mathrm{}t+t_w}{g[(s_1s_2)\mathrm{}t]}\frac{t_w}{g(\mathrm{}t)}\frac{1}{(s_1s_2)^\alpha }$$
(49)
as $`\mathrm{}t\mathrm{}`$. From Eqs. (41) and (48),

$`\underset{\genfrac{}{}{0pt}{}{\mathrm{}t\mathrm{}}{\mu ^{}=t_w/g(\mathrm{}t)}}{lim}C(s_1\mathrm{}t+t_w,s_2\mathrm{}t+t_w)`$ (50)
$`=`$ $`\underset{\genfrac{}{}{0pt}{}{\mathrm{}t\mathrm{}}{\mu ^{}g_r(s_1s_2)=\frac{s_2\mathrm{}t+t_w}{g[(s_1s_2)\mathrm{}t]}}}{lim}C(s_1\mathrm{}t+t_w,s_2\mathrm{}t+t_w)`$ (51)
$`=`$ $`\widehat{C}[\mu ^{}g_r(s_1s_2)].`$ (52)
It implies that the aging regime is the region where $`t_w/g(\mathrm{}t)`$ is finite. In this aging regime the slow-process limit of the correlation function in the integrand of Eq. (40) is a function of $`s_1`$ and $`s_2`$ if $`f(\mu )`$ in Eq. (41) is not a constant. It means that the work $`W_s`$ depends on $`h(s)`$.
4. When $`lim_\tau \mathrm{}\tau /g(\tau )=0`$ and $`lim_\tau \mathrm{}g(\tau )/g(s\tau )=\mathrm{}(s<1)`$, we prove below that the aging regime for experimental time scales does not exist. We assume that the aging regime exists. It means that a function $`p(t)`$ exists such that $`lim_{\genfrac{}{}{0pt}{}{\mathrm{}t\mathrm{}}{\mu =t_w/p(\mathrm{}t)}}(s_2\mathrm{}t+t_w)/g[(s_1s_2)\mathrm{}t]`$ is finite. Then, from the condition $`lim_\tau \mathrm{}\tau /g(\tau )=0`$,

$`\underset{\genfrac{}{}{0pt}{}{\mathrm{}t\mathrm{}}{\mu =\frac{t_w}{p(\mathrm{}t)}}}{lim}{\displaystyle \frac{s_2\mathrm{}t+t_w}{g[(s_1s_2)\mathrm{}t]}}`$ (53)
$`=`$ $`\underset{\genfrac{}{}{0pt}{}{\mathrm{}t\mathrm{}}{\mu =\frac{t_w}{p(\mathrm{}t)}}}{lim}{\displaystyle \frac{t_w}{g[(s_1s_2)\mathrm{}t]}}`$ (54)
$`=`$ $`\underset{\mathrm{}t\mathrm{}}{lim}{\displaystyle \frac{\mu p(\mathrm{}t)}{g[(s_1s_2)\mathrm{}t]}}.`$ (55)
Assuming that $`s_1^{}s_2^{}>s_1s_2`$, we see from the condition $`lim_\tau \mathrm{}g(\tau )/g(s\tau )=\mathrm{}(s<1)`$ that

$`\underset{\genfrac{}{}{0pt}{}{\mathrm{}t\mathrm{}}{\mu =\frac{t_w}{p(\mathrm{}t)}}}{lim}{\displaystyle \frac{s_2\mathrm{}t+t_w}{g[(s_1s_2)\mathrm{}t]}}/\underset{\genfrac{}{}{0pt}{}{\mathrm{}t\mathrm{}}{\mu =\frac{t_w}{p(\mathrm{}t)}}}{lim}{\displaystyle \frac{s_2^{}\mathrm{}t+t_w}{g[(s_1^{}s_2^{})\mathrm{}t]}}`$ (56)
$`=`$ $`\underset{\mathrm{}t\mathrm{}}{lim}{\displaystyle \frac{\mu p(\mathrm{}t)}{g[(s_1s_2)\mathrm{}t]}}{\displaystyle \frac{g[(s_1^{}s_2^{})\mathrm{}t]}{\mu p(\mathrm{}t)}}`$ (57)
$`=`$ $`\underset{\mathrm{}t\mathrm{}}{lim}{\displaystyle \frac{g[(s_1^{}s_2^{})\mathrm{}t]}{g[(s_1s_2)\mathrm{}t]}}`$ (58)
$`=`$ $`\mathrm{}.`$ (59)
Since Eq. (59) contradicts the assumption that $`lim_{\genfrac{}{}{0pt}{}{\mathrm{}t\mathrm{}}{\mu =t_w/p(\mathrm{}t)}}(s_2\mathrm{}t+t_w)/g[(s_1s_2)\mathrm{}t]`$ is finite, the aging regime for experimental time scales does not exist in this case. Hence, if only this aging regime characterized by such $`g(t)`$ exists, $`lim_{\genfrac{}{}{0pt}{}{\mathrm{}t\mathrm{}}{t_w\mathrm{}t}}C(s_1\mathrm{}t+t_w,s_2\mathrm{}t+t_w)`$ is equal to $`0`$ or $`q`$. It implies that the work is independent of $`h(s)`$. An example of such $`g(t)`$ is $`g(t)=\mathrm{exp}(t)`$.

Consequently, we conclude that if there are aging regimes characterized by $`g(\tau )`$ of case 2. or case 3. and the function $`\widehat{C}(\mu )`$ is not a constant and the FDT violation factor $`X`$ is not equal to $`0`$, the work for the slow process depends on the path of changing the external field $`h(s)`$. In this case, contrary to the fundamental assumption of thermodynamics, the work for the slow process is not the difference of a state function.

## V The work in the aging regime; results for single-correlation-scale systems and multi-correlation-scale systems

It has been explicitly checked on several disordered models that in the long-time limit two situations with different dynamical behavior seem to exist :

* There are systems with only one correlation scale apart from the quasiequilibrium regime, which we call “single-correlation-scale systems”. For these systems, the correlation function scales as $`C(t,t^{})=C[\xi (t)/\xi (t^{})]`$ and the FDT violation factor $`X`$ is a constant. Equilibrium states of these systems are solved by a one step replica symmetry breaking ansatz. Examples are the $`p`$-spin spherical spin-glasses  and a Lennard-Jones binary mixture which is a model of structural glasses in a glassy state . The real spin-glasses such as AgMn seem to belong to this class since it is known that the correlation function is scaled with single scaling function $`\xi (t)`$.
* There are systems such as Sherrington-Kirkpatrick (S-K) model which have an infinite number of correlation-scales apart from the quasiequilibrium regime , which we call “multi-correlation-scale systems”. For these systems, ultrametricity in time holds for any correlation such that $`C(t,t^{})<q`$; $`C(t_1,t_3)=\mathrm{min}[C(t_1,t_2),C(t_2,t_3)]\text{when}t_1>t_2>t_3\text{and}t_3\mathrm{}`$. The FDT violation factor $`X`$ is a nontrivial function of $`C`$. Equilibrium properties of these systems are solved by a full replica-symmetry breaking ansatz.

In this section, we analyze the path-dependence of the work for the slow process in the aging regime for these two classes of systems by using the general results obtained in the previous section, Sec. IV. It is important to note that only these two classes of systems seem to exist .

### A The single-correlation-scale systems

For the single-correlation-scale systems, scaling of the correlation function $`C(t,t^{})=C[\xi (t)/\xi (t^{})]`$ holds. Hence, the work for the slow process in the aging regime is given as

$`W_s/(\mathrm{}H)^2`$ $`=`$ $`{\displaystyle _0^1}𝑑s_1\dot{h}(s_1){\displaystyle _0^{s_1}}𝑑s_2\dot{h}(s_2)`$ (61)
$`\times \chi \{C[\underset{\genfrac{}{}{0pt}{}{\mathrm{}t\mathrm{}}{t_w\mathrm{}t}}{lim}{\displaystyle \frac{\xi (s_1\mathrm{}t+t_w)}{\xi (s_2\mathrm{}t+t_w)}}]\}.`$
Three explicit choices of the scaling function $`\xi (t)`$ have been proposed so far; $`\xi (t)=t,\xi (t)=\mathrm{exp}[(t/\tau _0)^{1\alpha }/(1\alpha )]`$ and $`\xi (t)=\mathrm{exp}[\mathrm{ln}^a(t/\tau _0)]`$ . We analyze below the properties of the work for the slow process for each three cases.

1. When $`\xi (t)=t`$, the correlation function decays in power-law as found in the trap model  and the $`p`$-spin spherical spin-glasses . The slow-process limit of the correlation function in Eq. (61) depends on $`s_1`$ and $`s_2`$ as

$$\underset{\genfrac{}{}{0pt}{}{\mathrm{}t\mathrm{}}{\mu =\frac{t_w}{\mathrm{}t}}}{lim}\frac{\xi (s_1\mathrm{}t+t_w)}{\xi (s_2\mathrm{}t+t_w)}=\frac{s_1+\mu }{s_2+\mu }.$$
(62)
This is an example of Eq. (46) in previous section.
2. When $`\xi (t)=\mathrm{exp}[\frac{1}{1\alpha }(\frac{t}{\tau _0})^{1\alpha }](\alpha <1)`$ , the slow-process limit of the correlation function in Eq. (61) depends on $`s_1`$ and $`s_2`$ through the scaling function which behaves as

$$\underset{\genfrac{}{}{0pt}{}{\mathrm{}t\mathrm{}}{\mu =t_w/\mathrm{}t^{1/\alpha }}}{lim}\frac{\xi (s_1\mathrm{}t+t_w)}{\xi (s_2\mathrm{}t+t_w)}=\mathrm{exp}[\frac{\mu }{\tau _0^{1\alpha }}(s_1s_2)].$$
(63)
This is an example of Eq. (52).
3. When $`\xi (t)=\mathrm{exp}[\mathrm{ln}^a(t/\tau _0)](a>1)`$ , the slow-process limit of the correlation function which appears in Eq. (61) depends on $`s_1`$ and $`s_2`$ through the scaling function which behaves as

$$\underset{\genfrac{}{}{0pt}{}{\mathrm{}t\mathrm{}}{\mu =\mathrm{}t/(t_w\mathrm{ln}^{1a}t_w)}}{lim}\frac{\xi (s_1\mathrm{}t+t_w)}{\xi (s_2\mathrm{}t+t_w)}=\mathrm{exp}[a\mu (s_1s_2)].$$
(64)
This is another example of Eq. (52)

To my knowledge, only three types of the scaling function $`\xi (t)`$ discussed above are known so far for single-correlation-scale systems. For each of three cases the slow-process limit of the correlation function in the integrand of Eq. (40) is a function of $`s_1`$ and $`s_2`$. It means for the single-correlation-scale systems that the work for the slow process in the aging regime depends on the path of changing the external field $`h(s)`$ and contrary to the assumption of thermodynamics the work for the slow process is not a difference of a state function.

In order to see more explicit form of the work for the slow process in the aging regime, we introduce the modified FDT Eq. (11) with constant violation factor $`X`$ which has been verified to be valid for the single-correlation-scale systems .

From Eq. (11), the susceptibility is given by

$$\chi (t,t^{})=\frac{1}{k_BT^{eff}}C(t,t^{})+\frac{q}{k_BT^{eff}}\frac{C(0)q}{k_BT},$$
(65)
where $`C(0)lim_t^{}\mathrm{}C(t^{},t^{})`$. Hence, from Eq. (40), the work for the slow process is given by

$`W_s/(\mathrm{}H)^2={\displaystyle \frac{C(0)q}{2k_BT}}{\displaystyle \frac{1}{k_BT^{eff}}}{\displaystyle _0^1}𝑑s_1{\displaystyle \frac{dh(s_1)}{ds_1}}{\displaystyle _0^{s_1}}𝑑s_2{\displaystyle \frac{dh(s_2)}{ds_2}}`$ (66)
$`\times \{q\underset{\genfrac{}{}{0pt}{}{\mathrm{}t\mathrm{}}{t_w\mathrm{}t}}{lim}C[\xi (s_1\mathrm{}t+t_w)/\xi (s_2\mathrm{}t+t_w)]\}.`$ (67)
Since $`lim_{\genfrac{}{}{0pt}{}{\mathrm{}t\mathrm{}}{t_w\mathrm{}t}}C(s_1\mathrm{}t+t_w,s_2\mathrm{}t+t_w)<q`$ when $`s_1s_2`$, the second term on the right hand side is non-zero. Hence, if $`T^{eff}`$ is finite the work for the slow process is not the difference of a state function since the work depends on the path of changing the field $`h(s)`$. In addition, the value of the work is different from the value of the work for the slow process in the quasiequilibrium regime: the first term on the right hand side of Eq. (67). In addition, it is also shown that since the correlation function is positive and smaller than the dynamical E-A order parameter in this regime, there are bounds for the value of the quasistatic work as

$$\frac{C(0)q}{2k_BT}\frac{q}{2k_BT^{eff}}\frac{W_s}{(\mathrm{}H)^2}\frac{C(0)q}{2k_BT}.$$
(68)
Eq. (68) shows that the work $`W_s`$ in the aging regime is independent of the path of changing the field and coincides with the work $`W_s`$ in the quasiequilibrium regime when the effective temperature $`T^{eff}`$ is infinite, which holds for the $`2`$-spin spherical spin-glass model  and a model of phase separation .

### B Possibility of observation of path-dependence

In the previous subsection, we saw that the work for the slow process depends on the path of changing the external field when $`\mathrm{}tt_w`$. We show here that the path-dependence of the work for the slow process is strong enough to be observed in experiments by evaluating the path-dependence of the $`5`$-spin spherical spin-glass model.

First, we describe the several pieces of information needed to evaluate Eq. (67). It is known that the scaling of the correlation function, such that $`C(t,t^{})q(t^{}/t)^\gamma `$ and the modified FDT with the effective temperature, i.e. Eq. (11), hold for the model . When $`k_BT/J=0.2`$ , $`\gamma 0.25`$ has been obtained. The dynamical E-A parameter $`q`$ and the effective temperature are given by $`q0.929`$ and $`T/T^{eff}0.227`$ when $`k_BT/J=0.2`$. In computation of these values, we uses the formulae:

$`q^3(1q)^2={\displaystyle \frac{(k_BT)^2}{10}},{\displaystyle \frac{T}{T^{eff}}}={\displaystyle \frac{3(1q)}{q}}.`$

In order to evaluate the magnitude of the path-dependence, we compute the relative difference between the works for two paths ($`h(s)=s`$ and $`h(s)=s^2`$) which is defined as the difference between the works for the two paths divided by the average of the two works. The results obtained from Eq. (67) are as follows; When the ratio of the measurement time to the waiting time is $`1:1`$, the relative difference is equal to $`0.037`$, i.e. about $`4\%`$; When the ratio is $`5:1`$, the relative difference is equal to $`0.094`$, i.e. about $`9\%`$.

Hence, we can say that the path-dependence of the work in the slow process can be observed for the $`5`$-spin spherical spin-glass model. The relative difference is plotted against the ratio of the waiting time to the measurement time in Fig. 4.

It tells that contrary to intuition the path-dependence becomes larger, as one increases the measurement time with keeping the waiting time fixed.

### C The multi-correlation-scale systems

For the multi-correlation-scale systems such as S-K model, it is known that the ultrametricity in time holds for all correlations such that $`C(t,t^{})<q`$ in the long-time limit ;

$$C(t_1,t_3)=\mathrm{min}[C(t_1,t_2),C(t_2,t_3)]\text{when}t_1>t_2>t_3.$$
(69)
By using this ultrametric relation Eq. (69), we prove below that the correlation function in the aging regime is a constant in the two cases (case 2 and case 3 in Sec. IV) where the work for the slow process can depend on the path of changing the external field $`h(s)`$. Thus, for these two cases, the work for the slow process is independent of the path $`h(s)`$. It has been proven in Sec. IV for the other two cases that the work for the slow process cannot depend on $`h(s)`$. Thus, the work for the slow process for the multi-correlation-scale systems is independent of the path of changing the field in all the experimental time regimes.

1. When $`g(\tau )=\tau `$, by substitution $`t_1t,t_2\mu ^{}t,t_3\mu t`$ in Eq. (69) and assuming that $`\mu ^{}>\mu `$, we see that

$$\underset{t\mathrm{}}{lim}C(t,\mu t)=\mathrm{min}[\underset{t\mathrm{}}{lim}C(t,\mu ^{}t),\underset{t\mathrm{}}{lim}C(\mu ^{}t,\mu t)].$$
(70)
Hence,

$$\underset{t\mathrm{}}{lim}C(\mu ^{}t,\mu t)=\underset{\mu ^{}t\mathrm{}}{lim}C(\mu ^{}t,\frac{\mu }{\mu ^{}}\mu ^{}t)=\stackrel{ˇ}{C}(\mu /\mu ^{})$$
(71)
where $`\stackrel{ˇ}{C}(\mu )lim_t\mathrm{}C(t,\mu t)`$. Thus, from Eq. (70),

$$\stackrel{ˇ}{C}(\mu )=\mathrm{min}[\stackrel{ˇ}{C}(\mu ^{}),\stackrel{ˇ}{C}(\mu /\mu ^{})].$$
(72)
Since it implies that

$$\stackrel{ˇ}{C}(\mu )=\{\begin{array}{cc}\stackrel{ˇ}{C}(\mu /\mu ^{})\hfill & \text{if }\mu ^2>\mu \hfill \\ \stackrel{ˇ}{C}(\mu ^{})\hfill & \text{otherwise,}\hfill \end{array}$$
(73)
$`\stackrel{ˇ}{C}(\mu )`$ is a constant and hence $`lim_{\genfrac{}{}{0pt}{}{\tau \mathrm{}}{\nu =t^{}/\tau }}C(\tau +t^{},t^{})=\stackrel{ˇ}{C}[\nu /(1+\nu )]`$ is a constant.
2. When $`lim_\tau \mathrm{}\tau /g(\tau )=0`$ and $`lim_\tau \mathrm{}g(\tau )/g(s\tau )g_r(s)(s<1)`$ exists, the ultrametric relation Eq. (69) is written as

$`\underset{\genfrac{}{}{0pt}{}{\tau \mathrm{}}{\mu =t^{}/g(\tau )}}{lim}C(\tau +t^{},t^{})`$ (74)
$`=`$ $`\mathrm{min}[\underset{\genfrac{}{}{0pt}{}{\tau \mathrm{}}{\mu =t^{}/g(\tau )}}{lim}C(\tau +t^{},t^{}),\underset{\genfrac{}{}{0pt}{}{\tau \mathrm{}}{\mu =t^{}/g(\tau )}}{lim}C(a\tau +t^{},t^{})]`$ (75)
where $`a`$ is a constant such that $`0<a<1`$. The second argument of $`\mathrm{min}`$ in Eq. (75) is rewritten as

$`\underset{\genfrac{}{}{0pt}{}{\tau \mathrm{}}{\mu =t^{}/g(\tau )}}{lim}C(a\tau +t^{},t^{})`$ $`=`$ $`\underset{\genfrac{}{}{0pt}{}{\tau \mathrm{}}{\mu =t^{}/g(a\tau /a)}}{lim}C(a\tau +t^{},t^{})`$ (76)
$`=`$ $`\underset{\genfrac{}{}{0pt}{}{\tau \mathrm{}}{\mu =t^{}/g(\tau /a)}}{lim}C(\tau +t^{},t^{})`$ (77)
$`=`$ $`\underset{\genfrac{}{}{0pt}{}{\tau \mathrm{}}{\mu =t^{}/[g_r(a)g(\tau )]}}{lim}C(\tau +t^{},t^{})`$ (78)
$`=`$ $`\underset{\genfrac{}{}{0pt}{}{\tau \mathrm{}}{\mu g_r(a)=t^{}/g(\tau )}}{lim}C(\tau +t^{},t^{})`$ (79)
$``$ $`\overline{C}[\mu g_r(a)],`$ (80)
where $`\overline{C}(\mu )lim_{\genfrac{}{}{0pt}{}{\tau \mathrm{}}{\mu =t^{}/g(\tau )}}C(\tau +t^{},t^{})`$. Similarly, the first argument of $`\mathrm{min}`$ in Eq. (75) is rewritten as

$`\underset{\genfrac{}{}{0pt}{}{\tau \mathrm{}}{\mu =t^{}/g(\tau )}}{lim}C(\tau +t^{},a\tau +t^{})`$ $`=`$ $`\underset{\genfrac{}{}{0pt}{}{\tau \mathrm{}}{\mu =(t^{}+a\tau )/g(\tau )}}{lim}C(\tau +t^{},a\tau +t^{})`$ (81)
$`=`$ $`\underset{\genfrac{}{}{0pt}{}{\tau \mathrm{}}{\mu =t^{}/g(\tau )}}{lim}C[(1a)\tau +t^{},t^{}]`$ (82)
$`=`$ $`\overline{C}[\mu g_r(1a)]`$ (83)
where the last equality is shown from Eq. (80). Consequently,

$$\overline{C}(\mu )=\mathrm{min}\{\overline{C}[\mu g_r(1a)],\overline{C}[\mu g_r(a)]\}.$$
(84)
Since $`g_r(a)>1`$, $`\overline{C}(\mu )lim_{\genfrac{}{}{0pt}{}{\tau \mathrm{}}{\mu =t^{}/g(\tau )}}C(\tau +t^{},t^{})`$ is a constant.

We proved above only that the correlation function is a constant within a correlation-scale since ultrametricity in time is valid within a correlation-scale. On the other hand, even for the multi-correlation-scale systems, the value of the correlation function becomes $`0`$ when the time difference is much larger than the waiting time. So, value of the correlation function must depend on an infinite number of correlation-scales. Hence, there is possibility that there is an infinite number of experimental time regimes characterized by different values of the work for the slow process.

## VI Discussion and conclusions

Summarizing our results, for systems with aging we have considered the experimental time scale dependence of the work exerted by modulating the external field in an isothermal process. We have shown that there are two experimental time regimes characterized by different behavior of the work. In the quasiequilibrium regime $`(\mathrm{}tt_w)`$, the work for the slow process is independent of the path of changing the external field and the value of the work for the slow process is different from the change of the Helmholtz free energy obtained by statistical mechanics with the assumption of ergodicity. When the process is not infinitely slow, the difference between the work for non-slow process and the work for the slow process is positive for any path of changing the filed, i.e. the principle of minimum work holds. In addition, we derived the dependence of the difference on the measurement time from the long-time behaviors of the correlation function.

In the aging regime $`(\mathrm{}tt_w)`$, whose precise meaning is given in Sec. IV, contrary to a fundamental assumption of thermodynamics, the work exerted in the slow process on the single-correlation-scale systems for which the FDT violation factor $`X`$ is not equal to $`0`$ depends on the path of changing the external field. It was examined that for the $`5`$-spin spherical spin-glass model the magnitude of the path-dependence is strong enough to be observed in experiments. The conditions when the work for the slow process depends on the path is also derived generally. On the other hand, for the multi-correlation-scale systems, the work for the slow process is independent of the path of changing the field. However, the work for the slow process still may depend on history of a system since there is possibility that there is an infinite number of experimental time regimes characterized by different values of the work for the slow process. In order to attack on this problem, information on time scale of the aging regime of multi-correlation-scale systems beyond time reparametrization invariance is necessary .

It is important to note that these results have a much broader range of validity, because they were derived without any assumption on microscopic properties of a system.

We consider the implications of our results on thermodynamics for systems with aging. In the quasiequilibrium regime, our results are the same as the consequences of thermodynamics, where the work for the slow process is independent of the path of changing the external field and the work for a non-slow process is larger than that for the slow process. Only discrepancy is difference between the value of the work for the slow process and that of the free energy obtained by statistical mechanics with the assumption of ergodicity. However, this discrepancy does not mean that the framework of usual thermodynamics is invalid since the free energy can be defined by the work for the slow process. This suggests the usual framework of thermodynamics is valid in the quasiequilibrium regime even though the system is out of equilibrium.

We considered only the properties of the work in the linear response regime. Thus, in order to prove validity of usual thermodynamics in the quasiequilibrium regime, the relation between the heat and the entropy has to be considered and extension of our analysis outside the linear response regime has to be performed. For these purposes, it would be interesting to analyze Langevin dynamics of spin-glass models with stochastic energetics .

Since the work for the slow process in the quasiequilibrium regime is independent of history of a system in linear response regime, it gives a fundamental state function for thermodynamics in the quasiequilibrium regime and is worth being measured in experiments. We discussed an experiment to measure it. Our results in Sec. III for the measurement time dependence of the work shows how long measurement time is needed to reach the expected accuracy.

However, since the waiting time can be long but should be finite in reality, the measurement time has to be finite in order to keep the experimental time scale in the quasiequilibrium regime. Otherwise the value of the work does not come close to that of the work for the slow process in the quasiequilibrium regime since the experimental time scale is in the aging regime. Hence, one cannot expect that the value of the measured work coincides with that of the work for the slow process with arbitrary accuracy. In other words, the accuracy of measurement of the state function is bounded by the length of the waiting time.

On the other hand, in the aging regime, our results imply that in contrast to the usual framework of thermodynamics it is essential to consider the experimental time scales such as the waiting time and the measurement time. Furthermore, history of a system as a state variable is necessary to describe thermodynamic properties of glassy materials. Although constructing thermodynamics for the aging regime is a tough work, it is a fruitful and challenging problem to be investigated since some universal properties in the aging regime are known . Recently, a framework of thermodynamics for the aging regime when the temperature changes in time is proposed . The framework avoids treating the problem of path-dependence by fixing a path to change the temperature. It is not clear whether thermodynamics for a single path to change the temperature is useful. Its validity and usefulness should be checked.

###### Acknowledgements.

I wish to acknowledge valuable discussions with Takashi Odagaki, Akira Yoshimori, Hiizu Nakanishi, Kazuo Kitahara, Osamu Narikiyo, Miki Matsuo, Ken Sekimoto, Shin-ichi Sasa, Yoshihisa Miyamoto, Hajime Takayama, Koji Hukushima and Hitoshi Inoue.

## A Derivation of the long measurement time behavior of $`WW_s`$

In this appendix, we derive the long measurement time behavior of the deviation from the work for the slow process for four types of relaxation of the correlation function described in Sec. III C.

### 1 The case where $`lim_t\mathrm{}t[C(t)q]`$ exists

In this section, we treat the case where $`lim_t\mathrm{}t[C(t)q]`$ exists, which includes the two cases where $`lim_t\mathrm{}t[C(t)q]`$ is equal to $`0`$ and where the limit is equal to a finite value $`c`$.

We rewrite the deviation given by Eq. (31) by introducing $`K(t)`$ defined as

$$K(t)_0^t𝑑\tau [C(\tau )q].$$
(A1)
The deviation is reduced to

$`{\displaystyle \frac{k_BT}{(\mathrm{}H)^2}}(WW_{qs})={\displaystyle \frac{1}{\mathrm{}t}}{\displaystyle _0^1}ds_1{\displaystyle \frac{dh(s_1)}{ds_1}}[h^{}(0)K(s_1\mathrm{}t)`$ (A2)
$`+{\displaystyle _1^{s_1}}ds_2h^{\prime \prime }(s_1s_2)K(s_2\mathrm{}t)].`$ (A3)
At first, we consider the deviation when $`lim_t\mathrm{}t[C(t)q]`$ is equal to $`0`$. Here, in order to prove that the deviation is proportional to the inverse of the measurement time $`\mathrm{}t`$, we show that the proportional constant is finite. The proportional constant is given as

$`\underset{\mathrm{}t\mathrm{}}{lim}\mathrm{}t{\displaystyle \frac{k_BT}{(\mathrm{}H)^2}}(WW_{qs})=\underset{\mathrm{}t\mathrm{}}{lim}{\displaystyle _0^1}ds_1{\displaystyle \frac{dh(s_1)}{ds_1}}[h^{}(0)K(s_1\mathrm{}t)`$ (A4)
$`+{\displaystyle _0^{s_1}}ds_2h^{\prime \prime }(s_1s_2)K(s_2\mathrm{}t)].`$ (A5)
Since $`lim_t\mathrm{}K(t)`$ exists in the case, $`K(t)`$ is finite. Hence, the order of the limit $`\mathrm{}t\mathrm{}`$ and the integration can be changed. Thus, the proportional constant is given by

$$\underset{\mathrm{}t\mathrm{}}{lim}\mathrm{}t\frac{k_BT}{(\mathrm{}H)^2}(WW_{qs})=K_{\mathrm{}}_0^1𝑑s\left|\frac{dh(s)}{ds}\right|^2,$$
(A6)
where $`K_{\mathrm{}}`$ is defined by Eq. (34). Consequently, it is proved that the proportional constant is finite and the deviation is proportional to $`1/\mathrm{}t`$.

Next, we consider the deviation when $`lim_t\mathrm{}t[C(t)q]`$ is equal to a finite value $`c`$. In order to prove that the deviation is proportional to $`\mathrm{log}\mathrm{}t/\mathrm{}t`$, we show that the proportional constant is finite. Dividing the region of integration of Eq. (A3) into five regions, the proportional constant is given by

$`\underset{\mathrm{}t\mathrm{}}{lim}{\displaystyle \frac{\mathrm{}t}{\mathrm{log}\mathrm{}t}}{\displaystyle \frac{k_BT(WW_{qs})}{(\mathrm{}H)^2}}`$ (A7)
$`=`$ $`\underset{\mathrm{}t\mathrm{}}{lim}{\displaystyle \frac{1}{\mathrm{log}\mathrm{}t}}[h^{}(0){\displaystyle _0^{\frac{1}{\mathrm{}t}}}ds_1h^{}(s_1)K(s_1\mathrm{}t)`$ (A8)
$`+`$ $`h^{}(0){\displaystyle _{\frac{1}{\mathrm{}t}}^1}𝑑s_1h^{}(s_1)K(s_1\mathrm{}t)`$ (A9)
$`+`$ $`{\displaystyle _0^{\frac{1}{\mathrm{}t}}}𝑑s_1h^{}(s_1){\displaystyle _0^{s_1}}𝑑s_2h^{\prime \prime }(s_1s_2)K(s_2\mathrm{}t)`$ (A10)
$`+`$ $`{\displaystyle _{\frac{1}{\mathrm{}t}}^1}𝑑s_1h^{}(s_1){\displaystyle _0^{\frac{1}{\mathrm{}t}}}𝑑s_2h^{\prime \prime }(s_1s_2)K(s_2\mathrm{}t)`$ (A11)
$`+`$ $`{\displaystyle _{\frac{1}{\mathrm{}t}}^1}ds_1h^{}(s_1){\displaystyle _{\frac{1}{\mathrm{}t}}^{s_1}}ds_2h^{\prime \prime }(s_1s_2)K(s_2\mathrm{}t)].`$ (A12)
We discuss the behavior of the function $`K(s\mathrm{}t)`$ in each region. When $`s1/\mathrm{}t`$, from the definition of $`K(t)`$, Eq. (34), it is shown that

$$K(s\mathrm{}t)_0^1𝑑\tau [C(\tau )q].$$
(A13)
Thus, $`K(s\mathrm{}t)`$ is finite even when $`\mathrm{}t\mathrm{}`$. On the other hand, when $`s>1/\mathrm{}t`$, we express the function $`K(s\mathrm{}t)`$ by using a function defined as $`C(t)qc/t+f(t),t1`$:

$`K(s\mathrm{}t)`$ $`=`$ $`{\displaystyle _0^{s\mathrm{}t}}𝑑\tau [C(\tau )q]`$ (A14)
$`=`$ $`{\displaystyle _0^1}𝑑\tau [C(\tau )q]+{\displaystyle _1^{s\mathrm{}t}}𝑑\tau [{\displaystyle \frac{c}{\tau }}+f(\tau )]`$ (A15)
$`=`$ $`{\displaystyle _0^1}𝑑\tau [C(\tau )q]+c\mathrm{log}s+c\mathrm{log}\mathrm{}t+{\displaystyle _1^{s\mathrm{}t}}𝑑\tau f(\tau ).`$ (A16)
Since $`lim_t\mathrm{}tf(t)=0`$, the fourth term on the right hand side is finite even when $`\mathrm{}t`$ is infinite. Thus, the behavior of the function is given as $`K(s\mathrm{}t)c\mathrm{log}\mathrm{}t`$ when $`s>1/\mathrm{}t`$. By evaluating the each term of Eq. (A12) with using the above behavior of the function $`K(s\mathrm{}t)`$, it is straightforward to show that

$$\underset{\mathrm{}t\mathrm{}}{lim}\frac{\mathrm{}t}{\mathrm{log}\mathrm{}t}\frac{k_BT}{(\mathrm{}H)^2}(WW_{qs})=c_0^1𝑑s|\frac{dh(s)}{ds}|^2.$$
(A17)
Consequently, it is proved that the proportional constant is finite.

### 2 The case where $`lim_t\mathrm{}t[C(t)q]`$ does not exist

In this section, we treat the case where $`lim_t\mathrm{}t[C(t)q]`$ does not exist, which includes the two types of long-time behavior of the correlation function, such that $`C(\tau )q+c/\tau ^\alpha ,0<\alpha <1`$ and $`C(\tau )q+c/\mathrm{log}\tau `$.

In order to find out the leading term in the behavior for the long measurement time, we divide the region of integration of Eq. (31) into three regions as

$`{\displaystyle _0^1}𝑑s_1{\displaystyle _0^{s_1}}𝑑s_2={\displaystyle _0^{(\mathrm{}t)^a}}𝑑s_1{\displaystyle _0^{s_1}}𝑑s_2+{\displaystyle _{(\mathrm{}t)^a}^1}𝑑s_1{\displaystyle _{s_1(\mathrm{}t)^a}^{s_1}}𝑑s_2`$ (A18)
$`+{\displaystyle _{(\mathrm{}t)^a}^1}𝑑s_1{\displaystyle _0^{s_1(\mathrm{}t)^a}}𝑑s_2,`$ (A19)
where we assume that the parameter $`a`$ satisfies $`0<a<1`$. Since all the integrands (the time derivative of the field and the correlation function) are finite, it can be shown that the first two terms on the right hand side are bounded as

$`|\text{the first term}|\text{const}\times (\mathrm{}t)^{2a}`$

and

$`|\text{the second term}|\text{const}\times (\mathrm{}t)^a[1(\mathrm{}t)^a].`$

In addition, we notice that since $`s_2s_1(\mathrm{}t)^a`$ in the region of integration of the third term, $`(s_1s_2)\mathrm{}t`$ is large when the measurement time $`\mathrm{}t`$ is large. Thus, the third term is determined by the long-time behavior of the correlation function.

At first, we treat the case where the correlation function behaves at a long time as $`C(\tau )q+c/\tau ^\alpha ,0<\alpha <1`$. We divide the region of integration of the third term of Eq. (A19) into three regions as

$`{\displaystyle _{(\mathrm{}t)^a}^1}𝑑s_1{\displaystyle _0^{s_1(\mathrm{}t)^a}}𝑑s_2={\displaystyle _0^1}𝑑s_1{\displaystyle _0^{s_1}}𝑑s_2{\displaystyle _0^{(\mathrm{}t)^a}}𝑑s_1{\displaystyle _0^{s_1}}𝑑s_2`$ (A20)
$`{\displaystyle _{(\mathrm{})^a}^1}𝑑s_1{\displaystyle _{s_1(\mathrm{}t)^a}^{s_1}}𝑑s_2.`$ (A21)
Since all the integrands are finite, it is shown that the last two terms are bounded by

$`|\text{the second term}|\text{const}\times (\mathrm{}t)^{a(2\alpha )\alpha }`$

and

$`|\text{the third term}|\text{const}\times (\mathrm{}t)^{\alpha a(1\alpha )}.`$

On the other hand, by using the long-time behavior of the correlation function, the first term is given as

$$_0^1𝑑s_1\frac{dh(s_1)}{ds_1}_0^{s_1}𝑑s_2\frac{dh(s_2)}{ds_2}\frac{c}{(s_1s_2)^\alpha }\frac{1}{(\mathrm{}t)^\alpha }.$$
(A22)
Thus, we find that this term is $`O[(\mathrm{}t)^\alpha ]`$. Assuming the free parameter $`a`$ is larger than the exponent $`\alpha `$, one sees that the leading term is Eq. (A22) by comparing the orders of all the terms in Eqs. (A19) and (A21). Hence, the long measurement time behavior of the deviation is given by Eq. (37).

Next, we consider the case where the long-time behavior of the correlation function is given by $`C(\tau )q+c/\mathrm{log}\tau `$. Again, we start by evaluating the third term on the right hand side of Eq. (A19). By using the long-time behavior of the correlation function, the term is given by

$$_{(\mathrm{}t)^a}^1𝑑s_1\frac{dh(s_1)}{ds_1}_0^{s_1(\mathrm{}t)^a}𝑑s_2\frac{dh(s_2)}{ds_2}\frac{c}{\mathrm{log}(s_1s_2)+\mathrm{log}\mathrm{}t}.$$
(A23)
Since in the region of integration the following inequality holds:

$`\left|{\displaystyle \frac{\mathrm{log}(s_1s_2)}{\mathrm{log}\mathrm{}t}}\right|a,`$

by neglecting numbers of $`O(a/\mathrm{log}\mathrm{}t)`$ the third term of the right hand side of Eq. (A19) is reduced to

$$_{(\mathrm{}t)^a}^1𝑑s_1\frac{dh(s_1)}{ds_1}_0^{s_1(\mathrm{}t)^a}𝑑s_2\frac{dh(s_2)}{ds_2}\frac{c}{\mathrm{log}\mathrm{}t}.$$
(A24)
Furthermore, by neglecting numbers of $`O[(\mathrm{}t)^a/\mathrm{log}\mathrm{}t]`$, the term is reduced to

$$_0^1𝑑s_1\frac{dh(s_1)}{ds_1}_0^{s_1}𝑑s_2\frac{dh(s_2)}{ds_2}\frac{c}{\mathrm{log}\mathrm{}t}=\frac{c}{2\mathrm{log}\mathrm{}t}.$$
(A25)
Consequently, one sees that the leading term is the above one by comparing the orders of all the terms in Eqs. (A19) and (A21). Thus, the long measurement time behavior of the deviation is given by Eq. (38).

Finally, in order to determine the order of the neglected term we determine the value of the free parameter $`a`$, since the neglected term contain the free parameter $`a`$. Since in terms of $`a`$ the order of the neglected terms are given as $`O(a/\mathrm{log}\mathrm{}t)`$ and $`O[(\mathrm{}t)^a]`$, we can determine the value of $`a`$ so that the value of the neglected terms are minimized. Thus, assuming that the neglected term is given by $`\alpha a/\mathrm{log}\mathrm{}t+\beta (\mathrm{}t)^a`$ where $`\alpha `$ and $`\beta `$ are constants, the value of $`a`$ is determined by

$$\frac{d}{da}[\alpha \frac{a}{\mathrm{log}\mathrm{}t}+\beta (\mathrm{}t)^a]=0.$$
(A26)
Since the solution is $`a2\mathrm{log}(\mathrm{log}\mathrm{}t)/\mathrm{log}\mathrm{}t`$, one sees that the order of neglected term is $`O[\mathrm{log}(\mathrm{log}\mathrm{}t)/(\mathrm{log}\mathrm{}t)^2]`$ as shown in Eq. (38).