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# Non-Thermal Chemistry in Diffuse Clouds with Low Molecular Abundances1

## 1 Introduction

Carbon is rarely found in the form of C I in the general interstellar medium (ISM). In the hot, ionized part of the ISM (like the interior of superbubbles), it is highly ionized, while in the warm neutral regions it is mainly in the form of C II. As the cloud gets colder the recombination of C II and the transition from C I to CO appears almost simultaneously (Hollenbach & Tielens 1999), leaving little room for C I as the dominant form of carbon. The diffuse clouds where this double transition usually occurs are very important for understanding the nature of atomic and molecular chemistry in the ISM. It is here where the important nonthermal effects, dissipation of turbulence (Duley et al. 1992; Falgarone, Pineau des Forêts, & Roueff 1995; Hogerheijde et al. 1995; Joulain et al. 1998; Pety & Falgarone 2000) and MHD waves (e.g., Draine & Katz 1986; Pineau des Forêts et al. 1986; Gredel, van Dishoeck, & Black 1993; Charnley & Butner 1995; Federman et al. 1996a), can seriously alter the chemical composition of the clouds. For example, it is not possible to understand the observed abundance of CH+ without taking into account these effects.

Our first objective is to derive the gas density and the kinetic temperature for such diffuse clouds. We infer this information from the observed populations among fine structure levels of the electronic ground state of C I. We searched the Hubble Space Telescope ($`HST`$) archive for spectra of bright stars known to show weak or moderate molecular absorption to minimize the effects of denser molecular cores. In all, we found nine suitable target stars; their properties from the Simbad database are listed in Table 1. The reddenings are from Savage et al. (1977). We included 23 Ori and $`\beta ^1`$ Sco (not listed in Table 1) in our sample with C I column densities from Federman et al. (1997).

The target stars are located in Taurus, Perseus, Orion, Scorpius, and Ophiuchus, with the exception of HD 112244. The general environment toward these stars is well characterized through numerous studies. $`\eta `$ Tau, for example, is one of the brightest members of the Pleiades (White 1984). Krelowski, Megier, & Strobel (1996) found two absorbing components toward the Perseus OB2 association, but simple molecules (CH, CN) could be detected only in one of them. UV observations of Martin & York (1982) and Vidal-Madjar et al. (1982) detected several absorption components toward the Perseus association. With the exception of one cold component, these were too weak and too hot to be observable in neutral carbon. The temperatures deduced by Trapero et al. (1992) from interstellar K I absorption toward stars in Perseus are in general agreement with the results of this study.

de Geus (1992) described the immediate vicinity of the Scorpio-Centaurus region in detail. He found that the ISM has been shocked and disturbed by the strong winds of O and B stars and past Type II supernovae from the numerous OB associations located here. A CO survey of the Ophiuchus region by de Geus, Bronfman, & Thaddeus (1990) found 5 main and several weaker cloud components. It is likely, however, that some of them are dense molecular cores not relevant for this study. High resolution spectroscopy of Na I D and K I $`\lambda `$7699 lines by Kemp, Bates, & Lyons (1993) revealed only 3 components, two stronger and one weak, in general agreement with our findings of two components. The more recent atomic surveys of Welty, Hobbs, & Kulkarni (1994) and Welty & Hobbs (2000) also indicate that our C I measurements probe the strongest components toward our sample of stars. $`Copernicus`$ observations of $`\sigma `$ Scorpii (Allen, Snow, & Jenkins 1990) revealed 4 components based primarily on H2 lines.

The main objective of this study is to obtain information on the importance of non–equilibrium CH+ chemistry for production of CH and CO in diffuse clouds. These molecules can be produced in very different environments. In the denser portions of a cloud they are involved in a complex thermal chemistry, while in warmer and more tenuous portions they are produced via CH+. Since any line of sight can involve several clouds and cloud sections, the inferred quantities and parameters are likely the result of several environments. If one can set up reasonable estimates of the contributions from the different environments, further constraints on the physical processes underlying nonthermal CH+ chemistry can be established.

We follow two approaches in our study. On the one hand, we estimate the amount of CH produced in denser regions (with equilibrium chemistry) and establish lower and upper limits on CH produced by the molecular chemistry. The difference between our limits and the observations should come from non-equilibrium chemistry, and this has to be accommodated by any model attempting to explain CH+ chemistry. On the other hand, we calculate CH and CO abundances arising from CH+ in diffuse clouds using the model of Federman et al. (1996a) to have a rough estimate of the amount coming from non-equilibrium chemistry. As an improvement on the models in Federman et al. (1996a), we use increased effective temperatures not only for ions, but also for neutrals directly produced by ion–ion or ion–neutral reactions. The effects on CH were noted by Gredel et al. (1993) and described in detail by Bucher & Glinski (1999).

Details of the data reduction and measurements are discussed in Section 2. The gas densities and temperatures were inferred from relative populations obtained by fitting synthetic spectra to the observations. We discuss this analysis in Section 3 and describe how the gas densities and temperatures were inferred from C I excitation in Section 4. We present the calculation of molecular abundances in Sections 5 and 6 for the equilibrium and non-equilibrium chemistry, respectively. We discuss our result briefly in Section 7 and summarize them in Section 8.

## 2 Measurements and Data Reduction

We retrieved observations for 9 new lines of sight from the $`HST`$ archive; most were acquired at medium resolution (MR; R=$`\frac{\lambda }{\mathrm{\Delta }\lambda }`$=20,000) and a handful were taken at high resolution (HR; R= 100,000). These spectra covered several C I multiplets and forbidden lines between 1150 Å and 1700 Å. The datasets that were retrieved from the $`HST`$ archive and used in our study are presented in Table 2.

We used the standard IRAF STSDAS package to cross-correlate and coadd the subexposures of the archival spectra. The most serious concern was an error in the background correction on some of our preprocessed data. We detected this error on all of our HR spectra containing the $`\lambda `$1260 multiplet of C I. The flux level of a strongly saturated line, such as those of S II and Si II, should be zero at line center; however, in some cases we measured negative or small positive values, clearly indicating an erroneous background correction. We could then apply an additional correction to compensate for the effect. We never encountered this problem on MR spectra although we had saturated lines in some cases, probably because scattered light was more easy to quantify in grating spectra.

After calibration and data reduction, the components in the neutral carbon lines were identified and the continuum of the background star was removed (continuum placement) by fitting it to a low order polynomial. The continuum placement turned out to be difficult for some multiplets, due to blending of several lines or simply because the lines were saturated. For example, in the vicinity of multiplet $`\lambda `$1260, Si II and Fe II lines seriously affected the continuum placement.

Following line identification and continuum placement, the Doppler shift (relative to the laboratory wavelength) and equivalent width ($`W_\lambda `$) of neutral carbon lines were measured. In some cases, only upper limits could be extracted from the average Full Width at Half Maximum (FWHM) of the instrumental function and the root mean square (rms) average of the noise in the stellar continuum ($`W_\lambda `$$`\times `$ FWHM $`\times `$ rms). The measured values of $`W_\lambda `$ are listed in Tables 11-19 in the Appendix for comparison with results of other investigations.

The $`HST`$ data for $`ϵ`$ Per and $`\omega ^1`$ Sco were supplemented with spectra for additional lines acquired with the $`Copernicus`$ satellite. These coadded spectra were obtained from the Multiwavelength Archive at the Space Telescope Science Institute (MAST). All spectra for each of the two directions were analyzed together.

## 3 C I Column Densities and Doppler Parameters

The column densities ($`N`$) and the Doppler parameters ($`b`$-values) that describe the absorbing components along each line of sight were determined by fitting synthetic profiles to the observed spectra. The synthetic fluxes were compared to the observations and the set of initial parameters was adjusted by a $`\chi ^2`$ minimization until a satisfactory fit to all observed spectra for a sight line could be achieved. Our approach was a modified second order gradient method, taken from Bevington & Robinson (1992). The program was tested by reproducing the results of curves of growth. We estimated the errors for the inferred parameters to be $``$ 10%, based on the goodness of the continuum placement and the noise in the spectra. The effects of other potential sources of error were negligible. For oscillator strengths, we used those from the compilation of Morton (1991), updated with our more recent astronomical determinations (Zsargó, Federman, & Cardelli 1997; Federman & Zsargó 2001).

Throughout the synthesis we used a Gaussian instrumental function with a FWHM of $``$ 3 km s-1 and $``$ 15 km s-1 for HR and MR spectra, respectively. The exact values of FWHM were calculated for each spectrum from the wavelength dependence in the resolution of Echelle-A and G160M (described in the instrumental handbook for the GHRS).

The results of the profile syntheses are shown in Table 3. To demonstrate the quality of fits that could be achieved by this procedure, we display observed and synthesized spectra for 1 Sco in Figure 1. The differences between the observed and model spectra in the Figure are well within the continuum noise for all C I multiplets. The HR spectra of $`\lambda `$ Ori, 1 Sco, $`\delta `$ Sco, and $`\sigma `$ Sco revealed that there are at least two components in C I absorption along these sight lines. The two components toward 1 Sco, for example, are clearly visible in the HR spectra of C I $`\lambda `$1328.83 in Figure 1. We could not discern multiple components toward most sight lines for which only MR spectra were available. The only exception is HD 112244 where the large separation ($``$ 24 km s-1) between the components was easily recognizable. The main absorption component (Component A) for the lines of sight in Table 3 are very well defined. The uncertainties in their columns and $`b`$-values are dominated by the errors in the continuum placement and by the signal-to-noise ratio of the spectra. The parameter values for the secondary components (Component B), on the other hand, are not defined very well. Often, we had to keep some parameters fixed during the synthesis in order to achieve reasonable values for the column densities, or else, only upper limits of $`N`$ could be provided.

Comparison between our line parameters and those extracted from high and ultra-high resolution measurements of atoms and molecules shows good correspondence. There are four sight lines with one C I component, $`\eta `$ Tau, $`ϵ`$ Per, $`\pi `$ Sco, and $`\omega ^1`$ Sco. The sight lines toward $`\eta `$ Tau and $`ϵ`$ Per indicate but one component in K I (Welty & Hobbs 2000) with $`b`$-values of about 1 km s-1. Presumably, the larger $`b`$-values in C I arise because this atom probes more widely distributed material. For $`\pi `$ Sco and $`\omega ^1`$ Sco, Welty et al. (1994) and Welty & Hobbs (2000) see multiple components in Na I D and K I, respectively. Here, our lower resolution measurements could not distinguish absorption from the stronger, closely spaced components. The $`b`$-values for the $`J`$ $`=`$ 0 lines reflect this. The narrower $`b`$-values for lines from $`J`$ $`=`$ 1 and 2 are likely the result of their sampling only the strongest component, a smaller portion of the line of sight, or both.

A similar pattern emerges for the sight lines with two C I components. The $``$ 12 km s-1 separation seen toward $`\lambda `$ Ori comes from the complexes discerned in Na I D measurements (Hobbs 1974; Welty & Hobbs 2000). Toward HD 112244, the two components about 24 km s-1 apart are also present in CH spectra (Danks, Federman, & Lambert 1984). For 1 Sco, the correspondence is seen in Na I D complexes (Welty et al. 1994; Welty & Hobbs 2000), separated by about 7 km s-1. The same applies to the two C I components ($`\mathrm{\Delta }v5`$ km s-1) toward $`\delta `$ Sco, which are present in Na I D and K I (Welty & Hobbs 2000) and CH+ (Crane, Lambert, & Sheffer 1995). Finally, the 9 km s-1 separation in components toward $`\sigma `$ Sco is seen in Na I D and K I (e.g., Welty & Hobbs 2000).

## 4 Excitation Analysis

We used the column densities found from the profile syntheses to infer gas densities and temperatures for the gas containing C I. To do so we assumed steady-state detailed balance among the fine structure levels $`J`$ $`=`$ 0, 1, and 2 of neutral carbon. Two independent number density ratios can be established. These are

$$\frac{n_{J=2}}{n_{J=0}}=\frac{R_{0,2}\left(A_{1,0}+R_{1,0}+R_{1,2}\right)+R_{1,2}R_{0,1}}{\left(A_{2,1}+R_{2,1}+R_{2,0}\right)\left(A_{1,0}+R_{1,0}+R_{1,2}\right)R_{1,2}\left(A_{2,1}+R_{2,1}\right)}$$
(1)
and

$$\frac{n_{J=1}}{n_{J=0}}=\frac{R_{0,1}\left(A_{2,1}+R_{2,1}+R_{2,0}\right)+R_{0,2}\left(A_{2,1}+R_{2,1}\right)}{\left(A_{2,1}+R_{2,1}+R_{2,0}\right)\left(A_{1,0}+R_{1,0}+R_{1,2}\right)R_{1,2}\left(A_{2,1}+R_{2,1}\right)},$$
(2)
where the terms $`R_{i,j}`$ are defined by

$$R_{i,j}=\underset{k}{}\gamma _{i,j}^kn_k+G_{i,j}.$$
(3)
The quantities $`\gamma _{i,j}^k`$ are the collisional excitation or de-excitation rate coefficients through collision with species k and $`G_{i,j}`$ are the ultraviolet radiative pumping rates between fine structure levels i and j. In eqns. 1 and 2, the quantity $`A_{i,l}`$ is the far infrared spontaneous decay rate from level i to level l. Variables $`n_k`$ are the number density of species k. For our lines of sight, collisions with H, He, and H2 were considered, since they are the most abundant species in diffuse interstellar clouds. The C I collisional de-excitation rate coefficients are listed in Table 4. The corresponding excitation rates can be calculated by the formula

$$\gamma _{j,i}^k=\gamma _{i,j}^k\frac{2i+1}{2j+1}e^{T_{i,j}/T},$$
(4)
where $`kT_{i,j}`$ and $`T`$ are the energy between states i and j and the gas temperature, respectively. The rates for C I collisions with H2 and H were taken from Schröder et al. (1991) and from Launay & Roueff (1977), respectively. The collisional rates for He were from Lavendy, Robbe, & Roueff (1991) and Staemmler & Flower (1991). Radiative pumping was neglected in our analysis because it has a negligible effect on the populations, unless the ultraviolet field is at least 10 times the strength of the average interstellar field.

If the clouds have close to uniform density and chemical composition, then

$$n_k\frac{N_kn}{N_H+N_{H_2}+N_{He}},$$
(5)
$$\frac{n_{J=1}}{n_{J=0}}\frac{N_{J=1}}{N_{J=0}}and\frac{n_{J=2}}{n_{J=0}}\frac{N_{J=2}}{N_{J=0}},$$

where the $`N`$-s are the column density of species k, hydrogen, H2, helium, or a C I fine structure level, and $`n`$ is the gas density. We calculated the fractional abundances for H and H2 using column densities from Savage et al. (1977) and we assumed that 10% of the material is He for all lines of sight.

After substituting eqn. 5 in eqns. 1 and 2, one has two equations for the unknown temperature and gas density. Unfortunately, the temperature and density solutions for eqns. 1 and 2 are not unique. One can find many density-temperature pairs to satisfy these equations for a specific $`\frac{n_{J=1}}{n_{J=0}}`$ or $`\frac{n_{J=2}}{n_{J=0}}`$ ratio. As a further complication, the uncertainties in the C I column densities introduce uncertainties in the C I level ratios; therefore, a density range rather than a given value satisfies eqn. 1 or 2 for a temperature. As a consequence of this ambiguity, numerous density-temperature pairs simultaneously satisfy eqns. 1 and 2. One needs independent density or temperature estimates to further confine the solutions.

The density–temperature solutions of eqns. 1 and 2 are displayed in Figure 2 for the main components of each sight line. The C I excitation analysis was supplemented by the temperature estimates of Savage et al. (1977) which were determined by H2 excitation analysis for the sight lines. Since the H2 temperatures of Savage et al. (1977) are valid only for the main components, we did not perform the C I excitation analysis for the secondary components. The sole exception is HD 112244 where the two components are fairly similar; therefore, the temperature estimate of Savage et al. (1977) most likely applies to both components. In Figure 2, each C I ratio resulted in two density–temperature curves corresponding to the maximum and minimum ratios that were allowed by the uncertainties in the C I column densities. Any density-temperature point between the solid or the dashed curves in Figure 2 is consistent with the observed C I $`J`$=0 and 1 or the $`J`$=0 and 2 column densities. Then, the region that is between all four curves contains all density-temperature pairs that are the simultaneous solutions to eqns. 1 and 2. However, Figure 2 also shows that the temperature values are not well defined for most sight lines. The allowed temperatures range between 30 and 200 K, and can be confined only by the estimates of Savage et al. (1977). For simplicity, we accepted as solutions all the density-temperature pairs in Figure 2 that lie within the thick rectangles. These regions provide the smallest independent density and temperature ranges that satisfy both eqns. 1 and 2 for the observed C I ratios and consistent with the H2 excitation temperatures. The derived density and temperature ranges are listed in Table 5. In the case of $`\eta `$ Tau, we chose to list only an upper limit for the density, since the lower limit is essentially zero.

## 5 CH Production in Moderately Dense Regions

To estimate the amount of CH produced in the denser regions in our sight lines, we followed the method described in detail by Federman et al. (1997). In their work, they only used the most important processes to find the analytic expression

$$x(\mathrm{CH})=\frac{0.67k_1x(\mathrm{C}^+)x(\mathrm{H}_2)n}{G(\mathrm{CH})}$$
(6)
that describes the CH fractional abundance. In eqn. 6 and all the following equations, $`k_i`$ denotes the rate coefficient for reaction i and the fractional abundance of a species y is $`x`$(y)= $`n`$(y)/($`n`$(H) + 2$`n`$(H2)). The terms $`n`$, $`n`$(y), and $`G`$(y) are the gas density, number density of species y, and the photodissociation rate for species y, respectively. The photodissociation rate includes grain attenuation of ultraviolet radiation which is approximated by $`\tau _{UV}`$ = 2$`A_V`$ (Federman et al. 1994). For the sight lines in Scorpius, which have larger ratios of total to selective extinction, a value of 1.4$`A_V`$ was adopted. One can invert eqn. 6 and solve for $`n`$ using the observed CH abundance for a comparison between the densities derived from C I excitation. We can also constrain our results for CH, using available upper limits for $`N`$(C2) and $`N`$(CN). In equilibrium, the fractional abundances are given by the following expressions (Federman et al. 1997):

$$x(\mathrm{C}_2)=\left(\frac{1}{0.67}\right)\left(\frac{k_2}{k_1}\right)\left(\frac{G(\mathrm{CH})}{G(\mathrm{C}_2)}\right)\left(\frac{x(\mathrm{CH})}{x(\mathrm{H}_2)}\right)x(\mathrm{CH})$$
(7)
and

$$x(\mathrm{CN})=\left(\frac{1}{0.67}\right)\left(\frac{k_4x(\mathrm{N})+0.045k_5x(\mathrm{C}^+)}{k_1x(\mathrm{C}^+)}\right)\left(\frac{G(\mathrm{CH})}{G(\mathrm{CN})}\right)\left(\frac{x(\mathrm{CH})}{x(\mathrm{H}_2)}\right)x(\mathrm{CH}).$$
(8)
The rate coefficients and photodissociation rates used in this analysis are given in Table 6. A detailed description of these coefficients is given by Federman et al. (1994) with updates in Pan, Federman, & Welty (2001). Table 7 lists the necessary fractional abundances and $`\tau _{UV}`$ calculated from $`E`$($`BV`$) values of Savage et al. (1977). The data for H2 and the carbon-bearing molecules, CH, C2, and CN, are from Savage et al. (1977) and Federman et al. (1994), respectively. The CO abundances are from recent analyses of $`Copernicus`$ spectra (Crenny & Federman 2001, private communication). We used the CH+ abundances of Federman (1982), Lambert & Danks (1986), and Price et al. (2001). The data for $`x`$(C+) are from Sofia et al. (1997), $`x`$(O) from Meyer, Jura, & Cardelli (1998), and $`x`$(N) from Lugger et al. (1978) and York et al. (1983).

We estimated the gas densities necessary to reproduce the observed CH columns in an environment in thermal equilibrium by inverting eqn. 6 and using the data in Tables 6 and 7. Such environments are very different from those required to produce the observed amount of CH+. The calculated upper limits on densities, as expected, are much larger than those found from C I excitation (see Section 5). The sole exception is $`\sigma `$ Sco, where the two densities are marginally consistent with each other. Since we chose lines of sight with no detectable C2 and CN absorption, densities of several thousand cm-3 are not realistic, and the values inferred from C I excitation are more appropriate. The clear inconsistency resulting from the two density calculations is a strong indication that non-equilibrium CH chemistry is important toward these stars. This contrasts with the results for the molecule-rich gas toward $`\zeta `$ Oph (Lambert et al. 1994) where the above calculation and the observations gave similar results.

Using $`x`$(C2) or $`x`$(CN) as well as $`N_{total}`$ from Table 7, we can estimate the column densities of CH associated with the equilibrium chemistry from eqns. 7 or 8. Then, a lower limit on the amount of CH associated with the non-equilibrium CH+ chemistry can be imposed by comparing the calculated amounts to the observed column densities. On the other hand, if we use the densities derived from C I excitation in eqn. 6, an upper limit on the amount of CH produced via CH+ can be obtained. In Figure 3 we display the results, normalized to the observed column of CH+. The triangles and downward-pointing arrows represent the measured values and upper limits of the $`N`$(CH)/$`N`$(CH+) ratios, respectively. Ranges indicate the normalized CH columns that are likely to be associated with the non-equilibrium CH+ chemistry. Again, the results in Figure 3 strongly suggest that non-equilibrium chemistry is indeed very important for the production of CH in molecule-poor sight lines, and in some cases, like that of 23 Ori, it is the dominant source for this molecular species.

A larger contribution from the non-equilibrium CH+ chemistry would be necessary if CH is effectively destroyed by reactions with atomic hydrogen (reaction 30 in Table 8) in the moderately dense regions along our sight lines. This reaction is thought to be suppressed by a reaction barrier (e.g., Mitchell & Deveau 1983); however, recent quantal calculations (Harding, Guadagnini, & Schatz 1993; van Harrevelt, van Hemert, & Schatz 2002) suggest that this may not be the case. Unfortunately, the rate coefficient for the reaction is not well defined for the gas temperatures relevant to the diffuse ISM, and the value of $`x`$(H) in the moderately dense regions is not known $``$ only line of sight averages are available. Therefore, the importance of the reaction, CH + H $``$ C + H2, could not be judged properly and the reaction was not included in eqns. 6 $``$ 8. If significant amounts of CH are destroyed through this reaction, our conclusion about the importance of non-equilibrium chemistry would be strengthened.

## 6 Nonthermal Chemistry in Diffuse Clouds

We used the chemical model of Federman et al. (1996a) to examine the effects of nonthermal motions on diffuse cloud chemistry. The origin of the nonthermal motion is assumed to be the result of the propagation of Alfvén waves, constantly entering the cloud from the intercloud medium. The dissipation of these waves is concentrated primarily in a diffuse cloud boundary layer, the transition zone between the cloud and the intercloud medium. The molecular abundances resulting from the Alfvénic driven nonthermal chemistry are calculated for this boundary layer, without considering any time dependence or attempting to describe any changes in physical or chemical conditions throughout the region. Instead, we impose a set of conditions for the clouds toward our sample of stars that are inferred from previous observations or are from the excitation analysis of neutral carbon.

In the chemical model we use a set of 16 atomic and molecular species closely related to CH+ chemistry. These are H, He, C, O, He+, C+, H2, CO, CH, OH, H2O, CO+, CH+, CH$`{}_{}{}^{+}{}_{2}{}^{}`$, CH$`{}_{}{}^{+}{}_{3}{}^{}`$, and HCO+. The set of molecules and chemical reactions was chosen so that it constitutes a closed system with reasonable assumptions on the physical conditions in diffuse clouds. The chemical reactions involved in this model are given in Table 8; the rate coefficients were taken from Federman et al. (1997) and Draine & Katz (1986), updated with information from van Dishoeck & Black (1988), Federman & Huntress (1989), Mitchell (1990), Anicich (1993), Millar, Farquhar, & Willacy (1997), and Pan et al. (2001). For example, the CO photodissociation rates come from the tabulation in van Dishoeck & Black (1988) using the observed column densities of CO and H2 and $`\tau _{UV}`$. The photodissociation rates for the other molecules included grain attenuation through the $`\tau _{UV}`$ values listed in Table 7. Abundances of CH, CO, CO+, HCO+, He+, CH$`{}_{}{}^{+}{}_{2}{}^{}`$, and CH$`{}_{}{}^{+}{}_{3}{}^{}`$ were calculated by solving a system of nonlinear rate equations. We assumed that for all lines of sight the He, OH, and H2O fractional abundances are 0.1, 1.6 $`\times `$ 10-10, and 3.2 $`\times `$ 10-11, respectively, based on the theoretical results of Federman et al. (1996b). The abundances of the remaining elements and molecular species, listed in Table 7, were taken from observations (see Section 5) and were kept fixed throughout the analysis. Fractional abundances of neutral carbon are from the present analysis. The electron densities were derived from the C+ abundances.

We define an effective temperature for each ion-neutral (and in some cases for each neutral-neutral) reaction in order to introduce the effects of nonthermal motions. Federman et al. (1996a) defined $`T_{eff}`$ as

$$\frac{3}{2}kT_{eff}=\frac{3}{2}kT+\frac{1}{2}\mu v_{particle}^2.$$
(9)
where $`k`$ and $`\mu `$ are the Boltzmann constant and the reduced mass of the system, respectively. The term $`v_{particle}`$ is the turbulent velocity of either the ionic ($`v_{ion}`$) or the neutral ($`v_{neutral}`$) species and defined by the root mean square Alfvén wave amplitude or zero, depending on the physical environment we attempted to model.

First, we tested our code by attempting to reproduce the results of Federman et al. (1996a). They imposed a set of conditions on their model clouds that are believed to be representative of the region in which the effects of nonthermal chemistry are significant. Therefore, we modeled their “hypothetical” cloud with fractional abundances of 0.2, 0.076, 2 $`\times `$ 10-4, 7.94 $`\times `$ 10-5, and 3.02 $`\times `$ 10-4 for H2, He, C+, N, and O, respectively. The visual extinction was set to 0.3 mag, representative of a predominantly atomic diffuse cloud, corresponding to a value of 0.6 for $`\tau _{UV}`$. Since we did not calculate CH+ abundances, as opposed to Federman et al. (1996a), we used their result for CH+ to calculate the amounts of CO+, HCO+, and CH produced by the nonthermal chemistry. The gas density, temperature, and $`v_{ion}`$ combinations used for the modeling correspond to their models 1, 2 and 3 $``$ (100 cm-3, 100 K, 3 km s-1), (50 cm-3, 100 K, 3 km s-1), and (200 cm-3, 100 K, 3 km s-1), respectively. In all cases the calculated CO+, HCO+, and CH abundances were within 30–40% of the values listed in Table 1 of Federman et al. (1996a).

In the models of Federman et al. (1996a), the nonthermal effects were considered only for charged species, reflecting the distinction that ions are tied to the magnetic field. However, if one considers the conservation of momentum during a chemical reaction, then it is plausible that the product species (ion or neutral) could carry some of the momentum from the parent molecules (Gredel et al. 1993; Bucher & Glinski 1999). This would mean that even neutral species, directly produced by reactions involving ionic species, can have more turbulent velocity than the average value for neutrals (not related directly to the ionic species). One could establish a complex model, where the turbulent velocity progressively decreases from the value representative for ions to that of the average for neutrals, following the chain of chemical reactions from ionic to neutral species. Such an approach is beyond the scope of this study. Instead, we simply explored the phenomena by setting the turbulent velocity for neutral molecules either to the ionic turbulent velocity or zero.

In our approach, we modeled three different situations, one with no turbulence at all (e.g. equilibrium chemistry), one with $`v_{ion}`$ 0 but $`v_{neutral}`$ $`=`$ 0, and one with nonzero $`v_{ion}`$ and $`v_{neutral}`$ $`=`$ $`v_{ion}`$. We used the equilibrium CH+ abundance of 3.3$`\times `$10-12 calculated by Federman et al. (1996a) whenever we attempted to model equilibrium chemistry without any turbulence. Since the observed CH+ abundance is primarily the product of non-equilibrium chemistry, we would introduce the effects of this chemistry into our “equilibrium” run ($`v_{ion}`$ $`=`$ 0 and $`v_{neutral}`$ $`=`$ 0) by using the observed amount of CH+. However, we used the observed amount of CH+ in the cases when the turbulent velocities were set to nonzero. The values for turbulent velocity were chosen to be the amplitude of Alfvénic waves. We adopted a standard value of 3 km s-1 for both $`v_{ion}`$ and $`v_{neutral}`$ (whenever they differ from zero), following Federman et al. (1996a), based on the typical width of CH+ absorption lines. We used the temperature and density from the C I excitation analysis (see Table 5) as $`T`$ and $`n`$.

The results of our calculations are shown in Tables 9 and 10 for CH and CO. It is immediately obvious that the observed abundances cannot be reproduced by equilibrium chemistry alone; there are several orders of magnitude difference between the observed and calculated abundances for all lines of sight for both CH and CO. Our results indicate that a nonthermal chemical model for ionic species only produces too much CH. When we also take nonthermal effects into account for neutral–neutral reactions, the observed CH abundances are reproduced reasonably well. The lone exception is the unusual line of sight toward 23 Ori, which has detectable amounts of CH and CH+ even though the H2 column is about 1018 cm-2. When $`T_{eff}`$ increases, reaction 17 (see Table 8) becomes more effective in destroying CH. This reaction also increases the amount of CO between models 2 and 3. Unlike the situation for CH, we did not find reasonable agreement for CO in general, indicating the limits of our approximations. The closest correspondence occurs for the denser sight lines, those in Scorpius, suggesting that pockets of higher density control the abundance of CO in diffuse gas. Since a theoretical determination of the rate coefficient for C+ $`+`$ OH $``$ CO+ $`+`$ H (Dubernet, Gargaud, & McCarroll 1992) suggests a value much larger than that used here, we investigated its affect on CO as well. While the equilibrium abundance for CO increases nearly 5 fold, the non-equilibrium results are changed only 5%. Clearly, the production of CO+ and HCO+, the precursors of CO, is dominated by the presence of enhanced amounts of CH+ brought about by non-equilibrium chemistry in the sight lines considered here. It is likely that we have to improve our model in other ways as well. For instance, a more precise description for $`v_{neutral}`$ is needed as is a more detailed analysis of H2 and CO photodissociation that includes self- and mutual–shielding.

## 7 Discussion

Observations and models have suggested long ago that the ISM is not in an equilibrium state. The underlying reason is that interstellar clouds cannot be treated as a closed systems; interactions with often violent surroundings are inevitable. Shock fronts from supernovae and cloud collisions are probably commonplace. These non-equilibrium processes affect the chemistry of most molecular species, including that of CH+. In fact, almost everyone agrees that these non-equilibrium processes hold the key for explaining the elusive CH+ abundance problem in the ISM. The exact mechanisms and place for CH+ production, however, is still the subject of intense debate. MHD shock models (e.g., Flower & Pineau des Forêts 1998) or those that involve intermittent dissipation of interstellar turbulence (e.g., Joulain et al. 1998) suggest that CH+ is formed in warm material at temperatures $`T>`$100 K. Excitation analysis of interstellar C2 (Gredel 1999), on the other hand, places the production of CH+ into the colder gas at temperatures of 50-100 K. Our results are more consistent with this later suggestion and support the claim that non-equilibrium chemistry is very important (or sometimes even dominant) for CH+, CH, and CO in diffuse sight lines. We concur with Gredell (1999) that about 30% of the observed CH is associated with CH+ synthesis. The associated molecular ions, CO+ and HCO+, are likely to be affected as well, with respective abundances reaching $`6\times 10^{13}`$ and about $`5\times 10^{11}`$. (We note in passing that such enhancements in the HCO+ abundance still yield column densities at least an order of magnitude below those inferred from absorption of the millimeter-wave continuum from extragalactic sources \[Lucas & Liszt 1996\].). This conclusion highlights the fact that any model attempting to account for CH+ abundances must address the “side-effects” on other species and be able to describe their abundances. Therefore, indirectly, we imposed constraints on the suggested theories thought to be responsible for CH+ production in this environment.

There were cases where our simplified models failed, indicating some shortcomings in our approach. It remains to be seen whether the source of these discrepancies is related to the assumed physical environment for particular lines of sight (gradients in physical conditions) or to effects ignored in our approach, such as detailed calculations for H2 and CO photodissociation. Another possible source of error is the “uniformity” of our approximations. The differences in $`b`$-values and Doppler shifts associated with the C I fine structure levels for a given sight line indicate that the levels might not fill the same volume. The excitation may occur in clumps. A more careful excitation analysis of neutral carbon is necessary to infer average density and temperature for diffuse clouds, but the means to perform such an analysis are beyond the capabilities of current theory and observation. Moreover, we either applied a given turbulence for neutrals or we did not. In reality, the turbulence can change gradually from the values representative for ions to that of neutrals as one follows the chemical network from an ionic parent molecule (like CH+ in our case) to products (Bucher & Glinski 1999). Further work should explore the importance of these various effects.

## 8 Summary

We surveyed the physical and chemical conditions in the diffuse ISM with the aim of assessing the importance of non-equilibrium processes. We retrieved a mixture of high and medium resolution spectra from the $`HST`$ archive. The selection criteria for the lines of sight was motivated by the idea to minimize the contribution from the denser diffuse cloud cores, which are satisfactorily described by equilibrium chemistry. We studied transitions involving the fine structure levels of neutral carbon to infer the physical parameters of these clouds through analysis of excitation. Our conclusions can be summarized as follows:

We could identify multiple cloud components along the sight lines for which high-resolution spectra were available and toward HD 112244 where the separation between the components was larger than the resolution of the MR spectra. We derived C I column densities and $`b`$-values for the components or provided upper limits for non-detections.

We performed C I excitation analyses for all main components to infer $`n`$ and $`T`$. The gas densities and kinetic temperatures were comparable to the representative values for diffuse clouds.

We calculated the abundances produced by molecular chemistry in the moderately dense regions along our sight lines. By removing the contribution from the molecular chemistry, we quantified the amounts of CH from nonthermal chemistry. Our analysis suggested that the amount of CH associated with CH+ is at least 30–40% of the amount of CH in general, but in some cases it can reach as high as 90% (e.g., 23 Ori).

Density estimates based on the observed upper limits for C2 and CN, along with CH columns, and on the assumption that the equilibrium chemistry acts alone were (much) larger than the densities from C I excitation. The discrepancy between these density estimates clearly indicates that the assumption of equilibrium chemistry as the sole contributor is inappropriate.

We modeled the non-equilibrium chemistry related to CH+ and improved upon the approximation of Federman et al. (1996a) to account for nonthermal motions, the driving force behind non-equilibrium chemistry. We defined effective temperatures for both ions and neutrals which involved thermal and nonthermal motions. We explored the effect of these motions with different combinations of neutral and ion turbulent velocities. We found that the observed amounts of molecular species cannot be reproduced by equilibrium chemistry. Models with non-zero turbulence for ions only also fail; turbulence for both ionic and neutral species was required to match the observations satisfactorily.

In closing, non-equilibrium chemistry is needed to explain the physical and chemical conditions in the diffuse gas toward our sample of stars and substantial amounts of CH are produced by nonthermal chemistry in the diffuse ISM along these sight lines.

A. Appendix

Here we present tables of equivalent widths for C I lines seen in our spectra (Tables 11-19). Comparison is made with other determinations, when available, and with the results of our profile syntheses. The agreement among the various measures is quite good, especially when one considers the fact that the MR spectra from $`HST`$ and the $`Copernicus`$ spectra do not always resolve blended lines or velocity components. Specific examples are given in the notes to each table.

We thank Dan Welty for his comments on the Ph.D. Dissertation from the Univ. of Toledo on which this paper is based. Comments by the anonymous referee improved several points in our paper. This research was supported by STScI grant AR-08352.01-97A. For the $`Copernicus`$ data, we utilized the archive developed by George Sonneborn and available at the Multiwavelength Archive at STScI. We made use of the Simbad database, operated at Centre de Donées Astronomiques de Strasbourg, Strasbourg, France.


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# Promiscuity and the Evolution of Sexual Transmitted Diseases

## Abstract

We study the relation between different social behaviors and the onset of epidemics in a model for the dynamics of sexual transmitted diseases. The model considers the society as a system of individual sexuated agents that can be organized in couples and interact with each other. The different social behaviors are incorporated assigning what we call a promiscuity value to each individual agent. The individual promiscuity is taken from a distributions and represents the daily probability of going out to look for a sexual partner, abandoning its eventual mate. In terms of this parameter we find a threshold for the epidemic which is much lower than the classical fully mixed model prediction, i.e. $`R_0`$ (basic reproductive number) $`=1`$. Different forms for the distribution of the population promiscuity are considered showing that the threshold is weakly sensitive to them. We study the homosexual and the heterosexual case as well.

We have introduced recently a model for the evolution of a sexual transmitted disease where the social behavior is incorporated by means of what we call the promiscuity variablegk02 , i.e. the daily probability of an agent to dismiss its permanent mate and go out to look for a sexual intercourse. The dynamics is of the SIR type: a susceptible (S) agent can become infected (I) after a sexual intercourse with an infectious one, with probability $`\beta `$ (the per sexual contact probability of get infected by an infectious agent). The infected individuals remain infectious for a period $`\tau `$, when they are removed (R) by death. The system will model the dynamic network of social contacts, where each element of the network is considered as a sexually active subject. The social behavior element is included via the promiscuity and the fraction of singles. In principle, individuals are grouped in couples and additionally a controlled proportion of singles, ($`\rho _s`$), is considered. The variable $`p_i`$, called the “promiscuity”, is what determines an individual’s tendency to dismiss his/her mate and go out –or just to go out in the case of the singles– to look for an occasional intercourse; more precisely $`p_i`$ is the probability of trying to meet an occasional partner on each intercourse opportunity or time step of the simulation (which, for the sake of simplicity, we take as a day). The $`p_i`$’s are randomly taken from a chosen distribution and assigned to each individual; we start with a semi-Gaussian distribution of width equal to $`\widehat{p}`$, but we will compare later others distributions. Those who happened to go out chose a partner at random and if the latter happened to go out too, the occasional couple is made. Therefore there is no social structure a priori. The web of contacts is constructed dynamically during the simulation depending on the percentage of singles and the population promiscuity. Most of the results are for the homosexual case, but we considered the heterosexual case too. The details of the simulation are given in gk02 , and the main result of this model can be expressed in the following relation, relating the four parameters of the model at the epidemic transition:

$$\widehat{p}_c^2\beta \tau =0.36,0.48,0.65$$

respectively for

$$\rho _s=0,0.5,1$$

where $`\widehat{p}`$ is a per day probability, $`\beta `$ is a per intercourse probability, and $`\tau `$ is in days. This relation gives us the following values for the mean promiscuity at the critical point: 0.025, 0.029, and 0.034, respectively for the three values of $`\rho _s`$, and for $`\beta =1`$ and $`\tau =1yr`$.

Some authors fh63 ; gra83 ; new02  have pointed to the connection between epidemics and percolation. In our case there is no network a priori, no topology with fixed links between nodes (agents); instead, the sexual network is continuously built and destroyed as time goes by, depending upon the individual promiscuity, that are controlled by the promiscuity distribution, and the fraction of singles. Therefore the threshold can be understood as a dynamic percolation. This is supported not only by the sharp transition of the asymptotic number of death at the critical promiscuity value, but by the divergence of the time needed to get that asymptotic number of death (remember that there is no other cause of death in the present model) at the same promiscuity value, as can be seen in Fig. 1. All of this has a strong resemblance with a percolation transition.

In the classical implementation of the SIR model (see Murray ), the dynamics of the susceptible, infectious, and removed classes is governed by the following ordinary nonlinear equations:

$$\frac{ds}{dt}=ris,\frac{di}{dt}=risai,\frac{dr}{dt}=ai$$

where $`r`$ is the infectious rate and $`a`$ is the removal rate per unit time; $`r`$ can be expressed as the product of $`\beta `$ and $`c`$, the mean number of sexual contact per unit time, and $`a`$ is the inverse of the infectious time $`\tau `$. The onset of the epidemic happens when the basic reproductive number $`R_0=\beta \tau c`$ is equal to 1. Therefore it is interesting to compare the threshold and the number of asymptotic death of the standard fully mixed model with the present results. In the former case we have to resort on numerical integration to solve the equations above. We do this up to a time were no new susceptible get infected (in practice when $`dS<1/N`$) and we plot the final number of removed agents against the average number of individual sexual contact per unit time, assuming that $`\beta =1`$ and $`\tau =1yr`$. The results are plotted in Fig 2 together with the prediction of our model. In order to do the comparison we have obtained from the simulations the relation between the average promiscuity and the average number of contacts per unit time (the latter depends almost quadratically on the former one).

Comparing them we see that the threshold predicted by the numeric solution of our model is considerably lower, possibly due to the effect of fluctuation that the uniformly mixed SIR model does not take into account. Moreover, the divergence between the latter and simulations increases when couples got into the scene. This more sophisticated version speed up the epidemic gk02 , so we conclude that the epidemic dynamics, in general, can not be reduced to take the average number of contacts as the only relevant parameter; as for our results, $`\rho _s`$ for example, is a relevant parameter too, and all of this reinforce the idea of using simulation as the appropriated technique to study epidemics.

The results summarized in Fig. 1 and Fig. 2 are for a semi-Gaussian distribution of promiscuity, so the natural question is “How sensitive to the choice of distribution are the results presented here?” In Fig. 3 we plot the results for a delta ($`p_i=`$ constant) and a uniform distribution together with the semi-Gaussian distribution, all of them normalized to the corresponding mean promiscuity $`p`$. We can see in Fig. 3 that the uniform and the semi-Gaussian distributions present almost the same threshold, while the delta distribution has its threshold slightly shifted to a larger promiscuity, due to the absence of heterogeneity. In the other hand we have previously shown gk02  that a power law distribution –more appropriated to the real word lens01 –, produce a contrary effect: a threshold shifted to a smaller promiscuity value. Nevertheless even in this latter case it is a weak effect, so we conclude that irrespective of the distribution of promiscuity, that in turn governs the distribution of contacts, the mean value is the most relevant measurements to mark the onset of the epidemic, while other moments (especially the standard deviation) seem not to be important, in contradiction with recent discussions ml01 ; ek02 ; lm01 .

A final word about the solution of the fully mixed classical implementation of the SIR model: generally speaking it is said that the limitation of this approach came from the fully mixed assumption and from assigning the same value of infectivity, and the same number of per year contacts to all individuals. However, apart from that limitations, there is one that comes first, it cames from the method of solution that assumes the population as continuous quantities without fluctuations. Let’s see: if we take the delta distribution, i.e. the same promiscuity for all agents, we have the model in the condition described above: each agent takes a potential partner at random from the whole population, so it is indeed fully mixed, and the parameters $`p,\beta `$, and $`\tau `$ are the same for everybody. However if we compare the curve of the classical SIR model solution of Fig. 2 with the results for the delta distribution in Fig. 3 the differences are obvious. Not only the threshold is overestimated by the classical approximation, the simulation predicts a sharp transition separating the no epidemic region from the epidemic one with no survivors at all. We emphasize that, apart from the limitation of the model, we are comparing here the exact solution of it (simulations) with an continuous -approximated- solution of the same model (the ODE equations)

So far we have assumed an heterogeneous population in terms of the promiscuity, but homogeneous on all of other respects, more appropriated for a gay community for example. What happens if we consider a heterosexual population? Taking the all married case version, but now 50% males and 50% females, we have the same output as for the homosexual case, as can be observed in Fig. 4. The point is that even when we have two subgroups in the population there is no asymmetry (the same promiscuity distribution, infectivity and,$`\tau `$ for all agents, whether they are males or females) so the results is no surprising. If we broke the symmetry we would expect a different behavior between the hetero and homo cases as we plan to study in the near future.

Summarizing we have presented some results for the spread of sexual transmitted diseases, based on a model that takes into account the social behavior. The model predicts a threshold condition quite different that what the classical SIR models predict. The onset of the epidemic is associated in the present model with a percolation threshold of a dynamical kind, because there is no static network of contact. The present model gives a direct connection between disease and social parameters and the outbreak threshold, which is quantitative equivalent to a basic reproductive number $`R_0=0.64`$, for the singles case (0.4 for the all married case), much lower than that of the fully mixed model prediction ($`R_0=1`$). On the other hand we have shown that the onset of epidemic depends mainly on the average number of contact, but seems to be independent of the exact form of the distribution, in opposition to recent analysis that include the second moment in the basic reproductive number of heterogeneous populations. Finally the threshold is sensitive to the fraction of singles, and this can have important consequences in modeling real data.

S.G. and M.K. acknowledge support from Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES, Brasil) and Secretaría de Ciencia, Tecnología e Innovación Productiva (SETCIP, Argentina).


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# Off Equilibrium Study of the Fluctuation-Dissipation Relation in the Easy-Axis Heisenberg Antiferromagnet on the Kagome Lattice

## Abstract

Violation of the fluctuation-dissipation theorem (FDT) in a frustrated Heisenberg model on the Kagome lattice is investigated using Monte Carlo simulations. The model exhibits glassy behaviour at low temperatures accompanied by very slow dynamics. Both the spin-spin autocorrelation function and the response to an external magnetic field are studied. Clear evidence of a constant value of the fluctuation dissipation ratio and long range memory effects are observed for the first time in this model. The breakdown of the FDT in the glassy phase follows the predictions of the mean field theory for spin glasses with one-step replica symmetry breaking.

Glassy systems are characterized by long relaxation times which increase at low temperatures and eventually exceed experimental observation times. At higher temperatures, the systems are ergodic and true equilibrium can be reached. However, below the glass transition temperature, $`T_g`$, the systems can become trapped in metastable states and often display strong non-equilibrium effects such as aging. The term aging refers to the fact that both static and dynamic properties depend on the time interval after which the system has been quenched into some non-equilibrium state. Structural glasses Gotze and Sjogren (1992) and spin glasses Bouchaud et al. (1998) exhibit these features and are essentially out of equilibrium on experimental time scales. In the case of spin systems, this behaviour is usually found in sytems with some type of quenched disorder. The disorder often imposes severe restrictions on the spin rearrangements and the evolution towards equilibrium requires many degrees of freedom to act cooperatively. The complexity of the phase space can lead to the violation of the fluctuation dissipation theorem (FDT) below a characteristic temperature.

In the last decade off equilibrium approaches have been used quite succesfully to describe systems which show a very slow dynamics Crisanti and Ritort (2002). A typical example is the zero-field cooling Lundgren et al. (1983) experiment, in which a sample is cooled in zero magnetic field to a low temperature at time $`t=0`$. After a waiting time $`t_w`$ a small magnetic field is applied and subsequently the time evolution of the magnetization is recorded. It is often observed that the relaxation of the magnetization becomes slower as the waiting time $`t_w`$ is increased. The system never reaches thermodynamic equilibrium and, consequently, time translational invariance (TTI) and the fluctuation dissipation theorem are no longer valid. However, the system is in a quasi-equilibrium state for time scales which are much longer than microscopic time scales but shorter than the relaxtional time scale of the slowly relaxing degrees of freedom. In this glassy regime a generalized form of the FDT has been proposed Cugliandolo and Kurchan (1993, 1994),

$$R(t+t_w,t_w)=\frac{X(t+t_w,t_w)}{T}\frac{C(t+t_w,t_w)}{t_w}$$
(1)
where $`C(t+t_w,t_w)`$ is a double time correlation function and $`R(t+t_w,t_w)`$ with $`t>0`$ is the associated conjugate response function. In this relation, $`T`$ is the heat bath temperature and the function $`X(t+t_w,t_w)`$ is called the fluctuation dissipation ratio (FDR) and is a measure of the departure from equilibrium. In the equilibrium regime, $`X`$ is equal to unity and the usual FDT is recovered. In the out of equilibrium regime, $`X`$ is generally less than unity. For large values of $`t`$ and $`t_w`$, it has been hypothesized Baldassari et al. (1995) that $`X`$ becomes a function of time only through the correlation function $`C`$ and a Quasi-FDT (QFDT) relation is obtained,

$$R(t+t_w,t_w)=\frac{X(C)}{T}\frac{C(t+t_w,t_w)}{t_w}$$
(2)
An important property of this function $`X(C)`$ is that it provides indirect information on the structure of the phase space. The ratio $`T_{eff}(C)=\frac{T}{X(C)}`$ has been interpreted Cugliandolo et al. (1997) as an effective temperature which is generally larger than the heat bath temperature $`T`$. This effective temperature has been used to classify glassy systems into three main groups: in models with a single pure state such as a pure ferromagnet Barrat (1998) and random Ising systems Parisi et al. (1999 and references therein), $`T_{eff}(C)`$ is infinite since $`X=0`$ ; in models of structural glasses Nicodemi and Coniglio (1997); Ricci-Tersenghi et al. (2000), Lennard-Jones glasses Parisi (1997); Barrat and Kob (1999) and $`p`$-spin models in $`d=3`$ Alvarez et al. (1996), $`T_{eff}(C)>T`$ is finite; in systems with full replica symmetry breaking as in several finite dimensional spin glasses Franz and Rieger (1995); Marinari et al. (1998); Parisi et al. (1998) and mean field (MF) models for spin glasses Takayama et al. (1997), $`T_{eff}(C)`$ is a nontrivial function of $`C`$.

Geometrically frustrated antiferromagnets can also exhibit glassy behaviour and other novel kinds of low temperature magnetic states Fazekas and Anderson (1974); Ramirez (1994); Zhitomirsky (2002) which are quite different from those observed in conventional magnets. Recently we have performed a numerical study of the two dimensional easy-axis Heisenberg antiferromagnet on the Kagome lattice Bekhechi and Southern (2003) by computing its static and dynamic properties. The magnetization indicates a finite $`T_c`$ but Monte Carlo snapshots of the individual spins below this temperature do not indicate any long ranged spatial order. Rather, the individual spins appear to be in a frozen state similar to a glass. The three spins on each elementary triangle form a distorted $`120^0`$ planar state with a net magnetization in the $`z`$-direction but there is no sublattice order. We extracted the critical temperature and the critical exponents associated with the magnetization, the susceptibility and the correlation length. We also studied the two-time spin-spin correlation function at high and low temperatures. We have found that non-exponential relaxation sets in at a temperature $`T^{}>T_c`$. The relaxation time increases according to a power law and diverges at a temperature $`T_g<T_c`$ where a transition to a glassy phase is located. Below $`T_g`$, we have found clear evidence for the presence of aging effects in the autocorrelation function from off-equilibrium dynamics. The aging effects obey the same scaling laws that are observed in spin glasses and polymers.

In this letter we report the first observation of the violation of the FDT in this low dimensional geometrically frustrated system without disorder. We determine both the FDR and the effective temperature $`T_{eff}(C)`$. Our results for $`X(C)`$ indicate that the system behaves like a generalized mean field model of glasses in which there is a one step replica symmetry breaking. In the aging regime, $`X(C)`$ has an approximate linear dependence on the temperature.

The Hamiltonian describing the model is,

$$H=J\underset{i<j}{}(S_i^xS_j^x+S_i^yS_j^y+AS_i^zS_j^z)$$
(3)
where $`(S_i^\alpha ,\alpha =x,y,z)`$ represents a classical three component spin of unit magnitude located at each site $`i`$ of a Kagome lattice. The number of sites $`N=3L^2`$ where $`L`$ is the linear size of the lattice and the exchange interactions are restricted to nearest-neighbour pairs of sites. The parameter $`A`$ describes the strength of the exchange anisotropy. In the following we restrict our consideration to the value $`A=2`$ which corresponds to the easy axis case.

In order to study the non-equilibrium properties of this easy axis frustrated system, we calculate the spin-spin autocorrelation function 111This is the same autocorrelation function studied in reference Bekhechi and Southern (2003) but the notation for the arguments is slightly different.

$$C(t+t_w,t_w)=\frac{1}{N}\underset{i}{}<S_i^z(t+t_w)S_i^z(t_w)>$$
(4)
where $`<\mathrm{}>`$ means an average over thermal histories and $`t_w`$ is the waiting time measured from some quenching time $`t_o=0`$. A second quantity of interest is the associated response function to an external magnetic field $`h_i(t)`$ applied at $`t_w`$,

$$M(t+t_w,t_w)=_{t_w}^{t+t_w}R(t+t_w,s)h(s)𝑑s.$$
(5)
The off equilibrium susceptibility $`\chi (t+t_w,t_w)`$ can obtained by dividing by the field magnitude and the QFDT relation (2) allows us to write for long times $`(t,t_w\mathrm{})`$

$$T\chi (t+t_w,t_w)=\frac{T}{h}M(t+t_w,t_w)=_{C(t+t_w,t_w)}^{C_0}X(C)𝑑C.$$
(6)
If the FDT is satisfied ($`X(C)=1`$), then we obtain the linear relation $`T\chi (t+t_w,t_w)=C_0C(t+t_w,t_w)`$. A departure from this straight line in a $`T\chi `$ vs $`C`$ parametric plot indicates a violation of the FDT and yields information about the function $`X(C)`$. In Ising systems, the upper limit $`C_0`$ in (6) is unity but in this Heisenberg system the value depends on both $`T`$ and the value of the easy axis anisotropy $`A`$. At $`T=0`$ it is given by $`C_0=\frac{(A+1)^2+2A^2}{3(A+1)^2}`$ but must be determined numerically at finite $`T`$.

For each Monte Carlo run, the system is initialized in a random initial configuration corresponding to a quenching from infinite temperature to the temperature $`T`$. We then allow the system to evolve for a time $`t_w`$ and we then make a second copy of the system. Using the original copy we compute $`C(t+t_w,t_w)`$ as a function of the observation time $`t>0`$, for different values of $`t_w`$ and $`T`$. In the second copy we apply a perturbation in the form of random small magnetic field $`h(i)=h^zϵ_i`$ in order to avoid favoring one of the different phases Barrat and Kob (1999). The $`ϵ_i`$ are taken from a bimodal distribution $`(ϵ_i=\pm 1)`$ and the strength of the field $`h^z`$ is taken to be small (typically between $`h^z`$=0.002 to 0.01) to ensure linear response. We compute the staggered magnetization in this second copy

$$M(t+t_w,t_w)=\frac{1}{N}\underset{i}{}\overline{<S_i^z(t+t_w)ϵ_i>},$$
(7)
whose conjugate field has magnitude $`h^z`$ and where the overline means an average over the random variables $`ϵ_i`$.

Typical data for the integrated response and the correlation function are shown in Fig. 1 where both functions exhibit a stationary part for at short times $`t<<t_w`$ and an aging part for $`t>>t_w`$. In Fig.2 , a parametric plot of the integrated response versus autocorrelation function is shown for $`T=0.04`$ obtained with a perturbing field magnitude $`h^z=0.01`$, for waiting times $`t_w=100,500,1000`$ and $`5000`$ Monte Carlo steps (mcs). It is clearly seen that for short times ($`t<<t_w`$) TTI and FDT hold and the straight line has a slope of $`1`$. For larger times ($`t>>t_w`$) a departure from the FDT line is observed indicating that the system has fallen out of equilibrium. A closer look at the data in the aging regime shows that , while the spin-spin autocorrelation function, $`C(t+t_w,t_w)`$ is decaying to zero as $`t\mathrm{}`$, the associated response function $`M(t+t_w,t_w)`$ keeps growing for all waiting times $`t_w`$ and its value depends on $`t_w`$. These features are reflected in a nontrivial function $`X(C)`$ . Similar curves have been obtained in previous studies of several glassy systems Ricci-Tersenghi et al. (2000); Parisi (1997); Barrat and Kob (1999); Alvarez et al. (1996) such as $`p`$-spin models and structural glasses.

The curves in Fig. 2 show a strong dependence on $`t_w`$, indicating that we are far from the asymptotic regime. This dependence on $`t_w`$ could possibly be explained by the fact that we are using waiting times that are too small Barrat and Kob (1999). Indeed, by performing simulations at a slightly higher temperature $`T=0.055`$ we see in Fig.3 that the curves clearly indicate: (i) two well separated time scales, (ii) no dependence of the FDR on $`t_w`$ in the aging regime, and (iii) no finite size effects. The presence of two time scales indicates that the system falls out of equilibrium at the point where the two straight lines intersect. If we identify this point with the $`t_w\mathrm{}`$ limit of the two-time autocorrelation function, then the FDR $`X(C)`$ can be described Alvarez et al. (1996) in the two regions as follows

$$T\chi (C)=\{\begin{array}{cc}C_0C,\hfill & Cq_{EA}\hfill \\ X[q_{EA}C]+[C_0q_{EA}],\hfill & Cq_{EA}\hfill \end{array}$$
(8)
where $`q_{EA}`$ is the value of $`C`$ at the crossing point and plays a role similar to that of the Edwards-Anderson order parameter in the mean field theory of spin glasses Franz et al. (1998). Fitting the data in the out of equilibrium regime to the straight line of eqn(8), will give us both the FDR $`X(C)`$ and $`q_{EA}`$.

The values of $`X(C)`$ and $`q_{EA}`$ obtained from this procedure are displayed in Fig. 4 as a function of $`T`$ using the data for $`t_w=2000`$ and $`L=60`$. We can see that at high temperatures $`X`$ is equal to $`1`$ and the usual FDT holds, whereas for $`T<T_{eff}`$ our results are well approximated by the straight line $`X(T)=T/T_{eff}`$ with $`T_{eff}=0.074\pm 0.001`$ . As the temperature increases the intersection point $`q_{EA}`$ decreases to zero with a sharp drop at $`T_{eff}`$ for this lattice size $`L=60`$. Our previous results Bekhechi and Southern (2003) for this model indicated a glass transition at a slightly lower temperature $`T_g=0.071\pm 0.002`$ where the relaxation time diverged. One would expect that $`T_{eff}>T_g`$ for systems with finite values of $`L`$ and $`t_w`$ and that it will approach $`T_g`$ for larger system sizes and longer waiting times. An extension of the present work to larger values of both $`L`$ and $`t_w`$ will also help to determine whether $`q_{EA}`$ approaches zero continuously or discontinuously at the glass transition.

In summary, we have shown that the fluctuation-dissipation ratio can be computed in this disorder free Kagome easy axis antiferromagnet. Several nontrivial features predicted by the mean field theory spin glasses are also present in this model. Namely, long-ranged memory effects and a constant FDR $`X(C)`$. These features correspond to a phase space structure similar to that of spin systems undergoing a one step replica symmetry breaking. The temperature dependence of the FDR $`X(T)`$ varies linearly with temperature $`X(T)=T/T_{eff}`$ as observed in binary mixtures of soft spheres Parisi (1997) and Lennard-Jones glasses Leonardo et al. (2000). All of our results are consistent with the existence of a glassy state at low temperatures in this geometrically frustrated model. The ideas developed for mean field descriptions of glassy systems seem to have an application far beyond the original models. Further experimental studies of these low dimensional frustrated magnets could provide some insight into the behaviour of glassy materials.

###### Acknowledgements.

This work was supported by the Natural Sciences and Research Council of Canada and the High Performance Computing facility at the University of Manitoba.


text:
# Quantum Dissipation due to the Interaction with Chaos

## Abstract

We discuss the possibility of having “quantum dissipation” due to the interaction with chaotic degrees of freedom. We define the conditions that should be satisfied in order to have a dissipative effect similar to the one due to an interaction with a (many body) bath. We also compare with the case where the environment is modeled by a random matrix model. In case of interaction with “chaos” we observe a regime where the relaxation process is non-universal, and reflects the underlaying semiclassical dynamics. As an example we consider a two level system (spin) that interacts with a two dimensional anharmonic oscillator.

The interaction of a system with its environment is a central theme in classical and quantum mechanics. The main effects that are associated with this interaction are “dissipation” (irreversible loss of energy) and “noise”. The latter is due to “fluctuations” of the environmental degrees of freedom. On short time scales the main effect is the “decoherence” due to the noise. On long time scales the interplay of dissipation and noise leads to a state of thermal equilibrium.

The common modeling of the system-environment interaction is provided by a Hamiltonian $`_{total}=_0+(Q,P;x)`$, where $`_0`$ is the system Hamiltonian, $`x`$ is a system observable, and $`(Q,P;x)`$ describes the environment including the interaction with the system. The simplest (and most popular) modeling of the environment is as a large collection of harmonic oscillators. This is known as the Caldeira-Leggett approach weiss ; leggett . Another approach is to use random matrix modeling of the environment mello ; pastur ; esposito . However, in this paper we are interested in another possibility, where the interaction is with (few) chaotic degrees of freedom.

In what follows “interaction with chaos” means that the environment is the quantized version of a few degrees of freedom chaotic system. This should be contrasted with “interaction with bath” where the environment is modeled as a large collection of quantized harmonic oscillators. Let us regard the environment as a “black box” (one does not know what is there). The questions that we would like to address are:  (1) How to characterize the bath in a way which does not assume a specific model.  (2) Is it possible to distinguish “interaction with chaos” from “interaction with bath”. As we explain below the second question is related to the notions of “thermodynamic limit” and “universality”.

Common models for dissipation assume a “thermodynamic limit”, which means interaction with infinitely many degrees of freedom. In this paper we inquire whether few chaotic degrees of freedom may have the same effect. This is a question of great practical importance. Future “quantum electronics” may consist of several interacting “quantum dots”. One wonders how a coherent process in one part of the “circuit” is affected by the ”noise” which is induced by the quantized chaotic motion of an electron in a nearby quantum dot. In other words: one would like to know whether it is possible to use in the nano-scale reality notions such as “dissipation” and “dephasing”, that are traditionally associated with having an interaction with many degrees of freedom.

As a specific example we consider a two level system (spin) that interacts with a two-dimensional anharmonic oscillator. This would be the well known “Spin-Boson” model weiss ; leggett  if the interaction were with a bath of harmonic oscillators. The motivation to deal with this model is well documented in the cited literature.

We also compare with the case where the interaction is with a random-matrix modeled environment. In the “quantum chaos” literature, and in mesoscopic physics, random matrix theory (RMT) is regarded as the “reference” case. Any deviation from RMT is called ”non-universality”, and has to do with the underlying semiclassical dynamics. In this paper we show that the notion of (non) universality can be extended into the studies of quantum dissipation.

The basic parameters that characterize any system-environment modeling are listed in Table 1. We shall define these parameters in a way which is independent of the theoretical modeling of the bath. A common assumption is going to be that the mean level spacing is very small. For completeness of presentation, and for the purpose of defining what does it mean “very small”, we keep $`\mathrm{\Delta }`$ as an explicit free parameter (note rmrk ).

| parameter | significance |
| --- | --- |
| $`\mathrm{\Delta }\mathrm{}^d`$ | environment mean level spacing |
| $`\mathrm{\Delta }_b\mathrm{}`$ | environment bandwidth |
| $`T`$ | environment temperature |
| $`d_\text{T}`$ | environment heat capacity |
| $`ϵ`$ | system energy |
| $`A`$ | system amplitude of motion |
| $`V`$ | system rate of motion |
| $`\mathrm{\Gamma }`$ | strength of coupling |

Table 1: The various parameters that characterize a generic quantum dissipation problem. (See text for details).

As a leading example we consider a two level system. For the system Hamiltonian we write $`_0=(\mathrm{}\mathrm{\Omega }/2)𝝈_1`$ where $`\mathrm{\Omega }`$ is the Bloch frequency, and $`𝝈_{i=1,2,3}`$ are the Pauli matrices. One can think of this Hamiltonian as describing a particle in a double well potential weiss ; leggett . Then it is natural to define its position as $`x=v𝝈_3`$, where $`v`$ is a constant. We assume that the interaction with the environment is via this “position” coordinate: $`(Q,P;x)=\frac{1}{2}(P_1^2+P_2^2+Q_1^2+Q_2^2)+(1+x)Q_1^2Q_2^2`$. This environment can be interpreted as a particle moving in a 2-dimensional anharmonic well (2DW). In the representation $`|\nu ,n`$, which is determined by $`(Q,P;0)`$ and $`𝝈_3`$, the Hamiltonian matrix takes the form

$`H_{total}=\left[\begin{array}{cc}𝑬+v𝑩& \mathrm{}\mathrm{\Omega }/2\\ \mathrm{}\mathrm{\Omega }/2& 𝑬v𝑩\end{array}\right]`$ (1)
where $`𝑬=\text{diag}\{E_n\}`$ is a diagonal matrix that contains the energy levels of the environment, and $`𝑩`$ is a banded matrix (see lds ). The initial state of the total Hamiltonian $`\mathrm{\Psi }(t=0)`$ is assumed to be factorized as $`\phi \psi `$, where $`\phi `$ is the initial state of the spin, and $`\psi =|n_0`$ is the initial state of the environment. It is implicit that we average over states with $`E_{n_0}E`$ corresponding to a microcanonical preparation. As for the spin, we would like to consider the standard scenario where the initial state is a coherent superposition $`|\phi =(|+|)/\sqrt{2}`$. The reduced probability matrix after time $`t`$ is

$`\rho _{\nu ,\nu ^{}}(t)={\displaystyle \underset{n}{}}\mathrm{\Psi }_{\nu ,n}(t)^{}\mathrm{\Psi }_{\nu ^{},n}(t)\frac{1}{2}(1+\stackrel{}{M}\stackrel{}{𝝈})_{\nu ,\nu ^{}}`$ (2)
where $`\stackrel{}{M}=(M_1,M_2,M_3)`$ is the polarization of the spin. It is most convenient to describe the state of the spin using $`\stackrel{}{M}`$. In particular we define $`S(t)=\stackrel{}{M}\stackrel{}{M}`$ as a measure for the purity of the spin state.

We turn to formulate the general case. The interaction of the system with the environment is assumed to be of the general form $`_{int}=x`$ where $`x`$ and $``$ are system and environmental observables respectively. (In the above example $`x=v𝝈_3`$ and $`=Q_1^2Q_2^2`$). In the absence of system-environment coupling we can characterize the fluctuations of the observable $`(t)`$ by a correlation function $`C(\tau )`$. (We are using here Heisenberg picture language). Its Fourier transform $`\stackrel{~}{C}_\text{E}(\omega )`$ is known as the power spectrum of the fluctuations. The observable $``$ has a matrix representation $`n||m=𝑩_{nm}`$ where we use the basis which is determined by $``$. The fluctuations are related to the bandprofile of this matrix:

$`\stackrel{~}{C}_\text{E}(\omega )`$ $`=`$ $`\left[{\displaystyle \underset{m}{}}\left|𝑩_{nm}\right|^22\pi \delta \left(\omega {\displaystyle \frac{E_mE_n}{\mathrm{}}}\right)\right]_{E_nE}`$ (3)
$``$ $`2\pi \sigma ^2\delta (\omega )+{\displaystyle \frac{2\pi \mathrm{}\sigma ^2}{\mathrm{\Delta }}}R\left({\displaystyle \frac{\mathrm{}\omega }{\mathrm{\Delta }}}\right)G\left({\displaystyle \frac{\mathrm{}\omega }{\mathrm{\Delta }_b}}\right)`$ (4)
In the first expression there is an implicit microcanonical averaging over the states $`E_nE`$. In the second expression $`\sigma ^2`$ is the average value $`\overline{|𝑩_{nm}|^2}`$, taken over the near-diagonal matrix elements. The lower cutoff function $`R()`$ depends on the level spacing statistics ophir : It is $`R()1`$ for $`\omega >\mathrm{\Delta }/\mathrm{}`$. The mean level spacing $`\mathrm{\Delta }`$ is proportional to $`\mathrm{}^d`$, where $`d`$ is the the number of environmental degrees of freedom. Any chaotic motion is characterized by a finite correlation time $`\tau _c`$. Therefore $`\stackrel{~}{C}_\text{E}(\omega )`$ has a a cutoff frequency $`\omega _c=2\pi /\tau _c`$. This implies (via Eq.(3)) that $`𝑩_{nm}`$ is a banded matrix with a bandwidth $`\mathrm{\Delta }_b=\mathrm{}\omega _c`$. The envelope function $`G()`$, with $`G(0)1`$, describes the bandprofile.

For sake of comparison we refer to the Spin-Boson model. The distribution of the bath oscillators is described leggett ; weiss  by a spectral function $`J(\omega )`$, leading to $`\stackrel{~}{C}_\text{E}(\omega )=2\mathrm{}J(\omega )/(1\text{e}^{\beta \mathrm{}\omega })`$, where $`\beta `$ is the reciprocal temperature of the bath. The “ohmic” assumption of having “white noise” ($`C(\tau )`$ with short correlation time $`\tau _c`$) for high temperatures is imposed by construction, by setting $`J(\omega )\omega G(\omega /\omega _c)`$. This corresponds to a strong chaos assumption. However, it should be realized that even if we “cook” a harmonic bath that has the same $`\stackrel{~}{C}_\text{E}(\omega )`$ as that of a chaotic environment, still there is a major difference: In spite of having the same bandprofile, the $`𝑩_{nm}`$ matrix of a harmonic bath is very sparse: only states that differ by “one photon” excitation of a single oscillator are coupled (hence the differences $`E_mE_n`$ are the frequencies of the harmonic oscillators).

In what follows we would like to define the notion of temperature ($`T`$) without assuming a specific modeling. There are three features of the environment that has to do with this notion: (i) The growing density of states; (ii) The growing fluctuations intensity; (iii) The asymmetry of $`\stackrel{~}{C}_\text{E}(\omega )`$ with respect to $`\omega `$. Let us regard the system as a “thermometer”. The equilibrium is determined by the microcanonical temperature $`T=(_E\mathrm{ln}(1/\mathrm{\Delta }))^1`$. For $`d=2`$ environment with constant density of states we would get $`T=\mathrm{}`$. \[We consider this hypothetical case for argumentation purpose. This would be indeed the case if the environment were modeled as a billiard. In a later paragraph we discuss the model of Eq.(1) for which $`T`$ is finite\]. In case of a two level system, having $`T=\mathrm{}`$ implies an equal probability for the two energy states. Now we can take (instead of a two level system) a particle with one degree of freedom as a “thermometer”. Since we already know that the “temperature” is (say) $`T=\mathrm{}`$, we may deduce that the friction coefficient, as determined by the fluctuation-dissipation theorem is $`\eta =\nu /(2T)=0`$, where $`\nu =\stackrel{~}{C}_\text{E}(\omega 0)`$ is the intensity of the fluctuations. This conclusion is wrong. In fact the friction coefficient is $`\eta =\frac{1}{2}\mathrm{\Delta }\times _E(\nu /\mathrm{\Delta })`$, as discussed in frc  (and references therein). Thus we can define an effective temperature, which is related to the thermalization process:

$`T_{\text{eff}}{\displaystyle \frac{\nu }{2\eta }}=\left({\displaystyle \frac{}{E}}\mathrm{ln}\left({\displaystyle \frac{1}{\mathrm{\Delta }}}\stackrel{~}{C}_\text{E}(\omega 0)\right)\right)^1`$ (5)
In generic circumstances the distinction between $`T_{\text{eff}}`$ and $`T`$ is not so dramatic. In fact, some further inspection into Eq.(3) reveals that generically $`T_{\text{eff}}=T/2`$. The above subtlety does not apply to a thermal preparation. Assuming a reciprocal temperature $`\beta `$, the friction coefficient (as obtained by canonical averaging over the above cited microcanonical result) is $`\eta =\frac{1}{2}\beta \nu `$. Therefore we get $`T_{\text{eff}}=1/\beta `$ as expected.

Having defined $`T`$, we can make a quantum mechanical distinction between high and low temperature regimes. This is related to the asymmetry of $`\stackrel{~}{C}_\text{E}(\omega )`$ with respect to $`\omega `$. Some inspection into Eq.(3) reveals that a finite temperature implies that the band profile acquires a factor $`\mathrm{exp}(\omega /(2T_{\text{eff}}))`$, which is consistent with the Spin-Boson modeling (see a previous paragraph). “High temperature” means that for the physically relevant frequencies $`\mathrm{}\omega /T1`$. A sufficient condition is $`T\mathrm{\Delta }_b`$. In the latter case $`\stackrel{~}{C}_\text{E}(\omega )`$ can be treated as a symmetric function with respect to $`\omega \omega `$, and therefore it can be interpreted as the power spectrum of a classical noise.

The issue of thermodynamic limit is related to the heat capacity of the environment. This is $`d_\text{T}=(T/E)^1d`$, where $`d`$ is its number of environmental degrees of freedom. The energy that the system can exchange with the environment is denoted by $`ϵ`$. If we want to assume a stable temperature $`T`$, the heat capacity of the environment should be large enough, so that energy exchange between the system and the environment does not have a big effect. This leads to the condition $`ϵd_\text{T}\times T`$. For a generic few degrees of freedom system $`ϵd_0\times T`$, where $`d_0`$ is the number of system degrees of freedom. This leads to $`d_0d_\text{T}`$. In case of a two level system the condition is much easier. Namely, we have $`ϵ\mathrm{}\mathrm{\Omega }`$, and therefore we get the “easy” condition $`\mathrm{}\mathrm{\Omega }d_\text{T}\times T`$.

Assuming the typical circumstances of an oscillating system, the time variation of the system observable $`x(t)`$ is characterized by an amplitude $`|x|A`$, and by a rate of change $`|\dot{x}|V`$. This specification of the system dynamics is essential in order to define a dimensionless parameter that characterizes the system-bath interaction:

$`{\displaystyle \frac{\mathrm{\Gamma }}{\mathrm{\Delta }}}=\text{minimum}({\displaystyle \frac{2\pi \sigma ^2}{\mathrm{\Delta }^2}}A^2,\left({\displaystyle \frac{\mathrm{}\sigma }{\mathrm{\Delta }^2}}V\right)^{2/3})`$ (6)
Loosely speaking this parameter indicates how many environmental energy levels are mixed non-perturbatively due to the interaction with the system. The $`A`$ dependence of $`\mathrm{\Gamma }`$ is the consequence of the well known theory by Wigner: It is the number of levels which are mixed by the perturbation in $`E_n\delta _{nm}+x𝑩_{nm}`$ with $`|x|A`$. If the perturbation is slow (small $`\dot{x}`$) this $`A`$ based estimate becomes non-relevant. For a proper analysis frc  one should switch to the adiabatic ($`x`$ dependent) basis, leading to $`E_n\delta _{nm}+\dot{x}(i\mathrm{}𝑩_{nm}/(E_nE_m))`$ with $`|\dot{x}|V`$. The $`V`$ based estimate for $`\mathrm{\Gamma }`$ follows from the latter representation. Thus one realizes that for slow rate of $`x`$ variation there is a crossover form a $`A`$-determined to a $`V`$-determined mixing.

The rest of this paper is aimed in clarifying the significance of the parameter $`\mathrm{\Gamma }`$. Some results of the simulations with the 2DW model Eq.(1) are presented in Fig.1. The energy of the environment was in the range $`2.8<E<3.2`$ where the classical dynamics is predominantly chaotic. The classical correlation time is $`\tau _c1`$. The simulations are done with $`\mathrm{}=0.03`$. This means that the bandwidth is $`\mathrm{\Delta }_b0.2`$. This should be contrasted with the mean level spacing $`\mathrm{\Delta }0.004`$. The temperature in the specified energy range is $`T1.3`$, and the heat capacity is $`d_\text{T}2.4`$. The amplitude of the motion is $`A=v`$, while the rate of the motion is formally $`V=\mathrm{}`$. The latter should be understood in the path-integral context (Eq.(7)), where $`x(t)`$ makes “jumps” between the two sites ($`x=\pm v`$). Hence $`\mathrm{\Gamma }(v/\mathrm{})^2`$. One can easily verify that the Kondo parameter leggett  is $`\alpha =(1/16\pi )\mathrm{\Gamma }/T`$. In our simulations $`\alpha 1`$.

In the lower panels of Fig.1 we present the corresponding results of simulations with a RMT model where the induced fluctuations have exactly the same power spectrum as in the 2DW model. The RMT model has been obtained by taking the Hamiltonian Eq.(1) with a randomized $`𝑩`$. We simply randomized the signs of the off-diagonal elements. This procedure destroys all the correlations between the elements, but does not affect the bandprofile (which is implied by Eq.(3)). Two observations should be made immediately: (i) A few degrees of freedom chaos indeed provides a dissipative effect, as in the case of a many degrees of freedom bath. (ii) The effect of interaction with “chaos” can be distinguished from the case of a random-matrix modeled environment. The latter claim is based on the observation that in the regime $`v>0.16`$ there is a two orders of magnitude difference between the corresponding curves. Also the scaling of curves with respect to $`v`$ is “broken” (upper panel): The sensitivity to $`v`$ is much smaller than implied by the overcompensating scaling of the time axis.

As explained in the introduction the deviation from RMT is regarded as “non-universality” and its understanding requires a proper definition of the classical limit. This should not be mistaken as a synonym for ”high temperatures”. The confusing, and possibly meaningless procedure to define this limit is by taking $`\mathrm{}0`$. We argue below that the meaningful definition of a “semiclassical regime” is by considering the nature of the dynamics of the environment. This leads to the condition $`\mathrm{\Gamma }\mathrm{\Delta }_b`$. In order to explain this condition we adopt the Feynman-Vernon picture of the dissipation process. Within this picture the propagator of the reduced probability matrix is written as a path integral:

$`K(\nu ,\nu ^{}|\nu _0,\nu _0^{})={\displaystyle \underset{x_A,x_B}{}}F[x_A,x_B]\text{e}^{i(𝒜[x_A]𝒜[x_B])}`$ (7)
The summation is over pairs of system trajectories (with weight factors absorbed into the definition of the integration measure). The action $`𝒜[x]`$ is defined as the phase which is accumulated along a given trajectory. We note that for a spin the trajectory is piecewise constant ($`x=\pm v`$). The influence functional is defined as $`F[x_A,x_B]=\psi |U[x_B]^1U[x_A]|\psi `$ where the expectation value is taken for the initial preparation of the environment (it is typically a mixture of many states implying that an appropriate average should be taken over $`\psi `$). The environmental evolution operator in case of the models that we consider is $`U[x]=𝒯\mathrm{exp}\left((i/\mathrm{})_0^t(𝑬+x(t^{})𝑩)𝑑t^{}\right)`$. Thus, in a semiclassical framework the problem of “quantum dissipation” reduces to that of analyzing “driven degrees of freedom”. It has been realized crs  that the driven dynamics becomes non-perturbative if $`\mathrm{\Gamma }>\mathrm{\Delta }_b`$. Below we discuss the implication of this observation.

The purity $`S(t)`$ is related to the dephasing factor $`|F[x_A,x_B]|`$. \[For $`\mathrm{\Omega }=0`$, the Hamiltonian Eq.(1) becomes block diagonal, leading to $`S(t)=|F[x_A,x_B]|^2`$, with $`x_A=v`$ and $`x_B=v`$\]. If the fluctuations are regarded as “noise”, one obtains the standard expression $`|F[x_A,x_B]|=\text{e}^{\frac{1}{2\mathrm{}^2}_0^t_0^tC(t^{}t^{\prime \prime })(x_B(t^{})x_A(t^{\prime \prime }))^2𝑑t^{}𝑑t^{\prime \prime }}`$. This expression implies a short time Gaussian decay $`S(t)=\mathrm{exp}(4C(0)(vt/\mathrm{})^2)`$, which evolves into a long time Gaussian decay $`S(t)=\mathrm{exp}((\sigma vt/\mathrm{})^2)`$ in the regime $`\mathrm{\Gamma }<\mathrm{\Delta }`$. If the envelope $`G()`$ of the bandprofile were smooth, then we would expect, in the regime $`\mathrm{\Delta }<\mathrm{\Gamma }<\mathrm{\Delta }_b`$, an intermediate stage of exponential decay $`S(t)=\mathrm{exp}(2\gamma t)`$ with $`\gamma =2(v/\mathrm{})^2\stackrel{~}{C}_\text{E}(\mathrm{\Omega })\mathrm{\Gamma }/\mathrm{}`$. In case of our numerical example the bandprofile has a structure lds , and hence $`C(\tau )`$ has oscillations that show up in the simulations.

Can we trust the standard expression for $`|F[x_A,x_B]|`$ if we have a dynamical environment rather than a noise source \[with the same $`C(\tau )`$\]? It is not difficult to observe that the standard expression can be derived from Fermi-golden-rule (FGR) considerations. In case of Harmonic bath the FGR treatment is valid, and this expression, with $`C(\tau )`$ replaced by its symmetrized version, is exact. But for interaction with ”chaos” we have claimed above that non-universality should show up in the non-perturbative regime ($`\mathrm{\Gamma }>\mathrm{\Delta }_b`$). Our numerics confirm this prediction: In the non-perturbative regime ($`\mathrm{\Gamma }>\mathrm{\Delta }_b`$) we find a premature ($`t<\tau _c`$) crossover from the expected short time Gaussian decay, to a non-universal behavior which is not captured by the standard formula. In the 2DW case the system has a classical limit, and therefore the nonperturbative decay of $`S(t)`$ is slowed down (compared with RMT) because it is limited by the classical dynamics. As observed (note the inset) the decay becomes much less sensitive to $`v`$.

The above discussed non-universality can be regarded as the manifestation of “semiclassical” correlations between the off-diagonal matrix elements of $`𝑩_{nm}`$. These are not reflected in $`\stackrel{~}{C}_\text{E}(\omega )`$. In case of the Spin-Boson model the $`𝑩_{nm}`$ matrix is sparse, which implies (in the limit of infinite bath) that off-diagonal correlations can be neglected. In case of a random matrix modeled environment, absence of correlations is guaranteed by construction for $`x=0`$, which implies (assuming no sparsity) lack of “invariance” with respect to $`x`$ kuzna . Accordingly we have three classes of models that become distinct in the non-perturbative regime.

In conclusion, we have discussed the consequences of having four energy scales $`(\mathrm{\Delta },\mathrm{\Delta }_b,T,\mathrm{\Gamma })`$ in any generic problem of “quantum dissipation”. The strength of the interaction is characterized by $`\mathrm{\Gamma }`$. A universal ”quantum dissipation” behavior requires a separation of energy scales $`\mathrm{\Delta }\mathrm{\Gamma }\mathrm{\Delta }_b`$. Non-perturbative breakdown of this universality due to the underlaying semiclassical dynamics is found if $`\mathrm{\Gamma }>\mathrm{\Delta }_b`$.

We thank M. Esposito, P. Gaspard, L. Pastur, and V. Falco for stimulating discussions. This work was supported by a Grant from the GIF, the German-Israeli Foundation for Scientific Research and Development, and by the Israel Science Foundation (grant No.11/02).

FIG.1: The decay of $`S\left(t\right)`$ in case of interaction with chaos (upper panels) and in case of interaction with a “randomized” environment that has exactly the same fluctuations (lower panels). The selected values of the coupling parameter are in the range $`10^4<v<0.3`$. The left panels are for the $`\mathrm{\Gamma }<\mathrm{\Delta }`$ regime ($`v<0.02`$) and for the $`\mathrm{\Gamma }>\mathrm{\Delta }_b`$ nonperturbative regime ($`v>0.16`$). The inset is for some of the $`v>0.16`$ curves without scaling. The arrows point on the largest $`v`$ value. The right panels are for the $`\mathrm{\Delta }<\mathrm{\Gamma }<\mathrm{\Delta }_b`$ regime ($`0.02<v<0.16`$). The scaling methods of the time axis are implied by the analysis of $`S\left(t\right)`$, which should hold if there is a universal behavior which is determined by $`C\left(\tau \right)`$ alone (see text).