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# Amplitude and frequency variability of the pulsating DB white dwarf stars KUV 05134+2605 and PG 1654+160 observed with the Whole Earth Telescope

## 1 Introduction

In recent times it has become clear that amplitude and frequency variations are common amongst pulsating stars. Various mechanisms for their explanation have been proposed. For example, resonant mode interaction (Moskalik 1985) is consistent with observations of this phenomenon in $`\delta `$ Scuti stars (e.g. Handler et al. 1998, 2000), whereas frequency changes of rapidly oscillating Ap stars may be attributed to variations in the magnetic field (Kurtz et al. 1994, 1997).

Time-resolved photometric observations of pulsating (pre-)white dwarf stars revealed that they are no exception in this respect. This bears a potentially enormous astrophysical reward: although these stars may only make part of their pulsation spectra observable to us at a given time, they may reveal their complete mode spectrum when observed persistently. Kleinman et al. (1998), Bond et al. (1996) and Vauclair et al. (2002) took advantage of this possibility and could then make seismic analyses for a pulsating DA white dwarf (G29-38) and two pulsating central stars of planetary nebulae (NGC 1501, RXJ 2117+3412). Without their amplitude variability, these stars would still be poorly understood.

Published reports of amplitude and frequency variations are still sparse for the Helium-atmosphere pulsating DB white dwarf stars (DBVs, see Bradley 1995 for a review), but so are their time-series photometric observations, mainly due to their faintness (most DBVs are around 16th magnitude). The glaring ($`B=13.5`$) exception is the prototype DBV GD 358 for which a plethora of measurements, including three Whole Earth Telescope (WET, Nather et al. 1990) runs, is available. Although the mode amplitudes of GD 358 vary, the associated pulsation frequencies seem reasonably stable (Kepler et al. 2002). Very recently, some amplitude and frequency variations have also been reported for the DBVs CBS 114 and PG 1456+103 (Handler, Metcalfe & Wood 2002).

We have started a systematic observing program to obtain reliable frequency analyses of the mode spectra of all pulsating DB white dwarfs. Our measurements consist of extensive single-site observations, which can suffice for very simply-behaved objects (Handler 2001), or low-priority WET observations (this paper), or even full worldwide multisite campaigns.

## 2 Observations and reductions

The pulsating DB white dwarf stars KUV 05134+2605 and PG 1654+160 were chosen as secondary target stars for the WET runs Xcov20 and Xcov21 during November 2000 and April 2001, respectively. Such secondary programme stars are observed by the network if the primary target is not observable or if two telescopes are on line and the larger one already measures the primary or if the observing method at a certain site is not suitable for the primary (e.g. CCDs are not proper instruments for very bright stars). Although the temporal coverage of the variations of a secondary target is usually considerably poorer than that of the primary, the resulting data sets are often quite valuable (see Handler et al. 1997 for an example).

In addition to the WET measurements, we acquired single-site observations of KUV 05134+2605 and PG 1654+160 before and/or after the main data stream. In an effort to understand these two stars to the limits currently possible, we also (re)analysed all available published and unpublished measurements. The time-series photometric data at our disposal are listed in Tables 1 and 2.

Most of the observations consisted of multichannel high-speed photoelectric photometry with 10-s integrations (see Kleinman, Nather & Philips 1996 for more information). Channel 1 measured the programme star, channel 2 measured a local comparison star, and channel 3 simultaneously recorded sky background. If no third channel was available, the measurements were irregularly interrupted to measure sky. Data reduction was performed with a standard procedure, as e.g. described by Handler et al. (1997).

Our CCD measurements were acquired with a number of different photometers – which we do not describe in detail here. The observations were optimised to acquire at least two local comparison stars in the same field as the target by minimising the readout time, ensuring a duty cycle as high as possible. In this way, consecutive data points were obtained in 10 \- 30 s intervals, depending on the instrument.

CCD data reduction comprised correction for bias, dark counts and flat field. Photometric measurements on these reduced frames were made with the programs MOMF (Kjeldsen & Frandsen 1992) or RTP (Østensen 2000), and differential light curves were created. No variability of any star other than the targets in the different CCD fields was found, and the comparison star ensemble resulting in the lowest scatter in the target star light curves was chosen.

At this point it should be noted that PG 1654+160 has a companion star (Zuckerman & Becklin 1992) at a separation of about $`4^{\prime \prime }`$ distance that may affect our measurements. Fortunately for us, this companion is very red. Consequently, we used red-cutoff filters, e.g. a Schott BG 39 glass, which suppressed the companion’s contribution sufficiently (it then was $``$2 mag fainter than the target), but did not waste too many photons of the target star. This also means that the companion’s flux did not affect the amplitudes of the photoelectrically measured target star light curves significantly, as all our photomultipliers are blue-sensitive.

Finally, the times of measurement were transformed to Barycentric Julian Ephemeris Date (BJED); the barycentric correction was applied point by point. Finally, some overlapping portions of the combined light curves were merged, and the reduced time series were subjected to frequency analyses.

## 3 Frequency analysis

Our frequency analyses were mainly performed with the program PERIOD 98 (Sperl 1998). This package applies single-frequency power spectrum analysis and simultaneous multi-frequency sine-wave fitting. It also includes advanced options, such as the calculation of optimal light-curve fits for multi-periodic signals including harmonic, combination, and equally spaced frequencies, which are often found in the analysis of the light curves of pulsating white dwarf stars.

In one case to be indicated later, this method was supplemented by a residualgram analysis (Martinez & Koen 1994), which is based on a least-squares fit of a sine wave with $`M`$ harmonics. One advantage of this method is that alias ambiguities can be evaluated more reliably by the simultaneous inclusion of the information in the Fourier harmonics.

### 3.1 KUV 05134+2605

We first analysed the WET measurements of KUV 05134+2605 with PERIOD 98. We computed the spectral window of the data (calculated as the Fourier Transform of a noise-free sinusoid with a frequency of 1.902 mHz and an amplitude of 9.7 milli-modulation amplitudes111One milli-modulation amplitude is the Fourier amplitude of a signal with a fractional intensity variation of 0.1%; it is a standard unit for WET data analysis. (mma)) followed by the amplitude spectrum itself. The results are shown in the upper two panels of Fig. 1. As the WET measurements were only acquired from North American observatories (a result from the star having second priority), the window function is poor.

Still, we show some prewhitening steps in consecutive panels in Fig. 1. This has been done to indicate the main regions in which pulsational signals are present, but definite periods cannot be determined. In any case, it is suggested that KUV 05134+2605 has a rich pulsation spectrum.

This is not the only interesting feature of the pulsations of the star: in the discovery paper (Grauer et al. 1989) it was found to be of much higher amplitude and longer period compared to its pulsational state during the WET run. The star has changed from showing dominant pulsations with time scales of 710 s and peak-to-peak amplitudes up to 0.2 mag to less than 0.1 mag and a dominant 530-s time scale (Fig. 2).

We have therefore calculated amplitude spectra of all the available data (Fig. 3). Interestingly, the amplitude spectrum of the star was different every time it was observed. Besides the data discussed before, the measurements from 1992 show a dominant variability time scale of around 650 s, and the February 2001 data have a prevailing time scale of 570 s. Only the light curves from October 2000 appear similar to those acquired by the WET some 6 weeks later, but this actually only applies to the signal of highest amplitude. We conclude that KUV 05134+2605 shows notable amplitude variability on time scales as short as 6 weeks. We cannot make any statement about frequency/phase variability as our data sets are too small to distinguish this hypothesis from the effects of beating between several signals.

We can attempt to construct the complete mode spectrum of the star by combining the results of the different observing seasons. Of course, all the data sets are affected by aliasing and no definite periods can be determined, but approximate periods in the different regions of power in the Fourier spectra that are separated by more than the width of the envelope of the corresponding spectral window, can be estimated. We summarize these results, omitting possible combination frequencies, in Table 3. The amplitudes in this table must be taken with some caution, as they could be affected by insufficient frequency resolution in some of the data sets.

As already noted, there is no correspondence between the period of the dominant modes in each of the subsets of data except for the two closest in time (October/November 2000). It almost appears that we looked at a different star every time KUV 05134+2605 was observed!

In any case, we tried to find the signatures of non-radial gravity (g)-mode pulsations from Table 3, also with the help of Fig. 4, where we plot the detected periods over the different observing seasons. However, equally spaced periods suggestive of the presence of a number of radial overtones of the same $`\mathrm{}`$ or equally spaced frequencies that might be due to rotational $`m`$-mode splitting were not detected.

We can therefore summarize the frequency analysis of KUV 05134+2605 as follows: it has a very rich mode spectrum and its pulsation amplitudes are highly variable. We cannot find a stable pulsational signal which would allow us to estimate an evolutionary period change. Only a dedicated multisite campaign would help to understand this star.

### 3.2 PG 1654+160

We again start the frequency analysis with the WET measurements. The spectral window and amplitude spectrum of these data are shown in Fig. 5. Although the amplitude spectrum does not appear very complicated, attempts to determine the underlying variations by prewhitening result in a large number of signals that seem to be present.

However, assuming that we deal with normal-mode pulsations of the star, the number of signals becomes unrealistically large, and some of the frequencies found that way are too closely spaced to be resolved within our data set. All this suggests that the amplitude spectrum of PG 1654+160 was not stable throughout the observations.

Consequently, we attempted to follow the suspected amplitude and frequency variability throughout the data set with various methods but again had to realize that our temporal coverage is insufficient for a detailed analysis. Some results can however be obtained:

* The longer period pulsations ($`P\stackrel{>}{}700`$ s) show a larger degree of instability;
* The amplitude spectrum was more stable during the second part of the run (beginning with April 25);
* Amplitude variability alone is insufficient to account for the observed variations; the pulsation frequencies also appear somewhat variable;
* The periods of the strongest signals can be determined, albeit with large errors due to the instability and aliasing.

The periods we could determine are listed in Table 4, together with the results from the other data sets to which we now turn.

In the same fashion as in the previous section, we computed amplitude spectra of all our data sets over the years. We show them in Fig. 6 which demonstrates that the pulsational behaviour of PG 1654+160 is also highly variable in time; a comparison of light curves is shown in Fig. 7. The time scales of the amplitude variations of PG 1654+160 can be as short as two weeks: the strong 913-s signal in the May 2001 data was absent in the previous WET data.

We determined the dominant periods in the different data sets, and summarize them in Table 4. Again, the amplitudes may be affected by resolution problems, and possible combination frequencies were excluded. In addition, there is good evidence for more signals being present in several of the data sets, but it is not possible to determine their periods and amplitudes reliably.

Some comments are necessary: the two strongest modes in the single-night data set from June 1985 are not resolved, which is why we cannot determine error estimates for their periods and thus disregard them for the following analysis. The errors on the other frequencies in this data set were assumed to be $`1/4T`$, where $`T`$ is the length of the run. For the other data sets, the errors on the periods include some possible alias ambiguities. In the April 1994 data, the 2-f harmonic of the dominant periodicity is also present. We therefore used the residualgram method (as described before) with $`M=2`$ to obtain a more reliable determination of this period before searching for more signals.

It is interesting to note that some periodicities in Table 4 occur in more than one data set. We have displayed these results graphically in Fig. 8, where we again show the detected periods over the different observing seasons. We note that the shorter periods ($`P<800`$ s) in the light curves of PG 1654+160 appear very consistently in the same regions, whereas the longer periods do not show that much regularity. However, the errors in the determination of those periods are also larger. Finally, the previously mentioned shorter-period signals seem to have an approximately equidistant spacing of about 40 s, and again our data show no sufficiently stable modes to estimate the evolutionary period change rate.

## 4 Discussion

We have shown that the amplitude spectra of both KUV 05134+2605 and PG 1654+160 are variable in time. Whereas we cannot find an underlying pattern in the periods of KUV 05134+2605, the roughly equidistant spacings within the shorter periods of PG 1654+160 suggests the presence of a number of radial overtones of g-modes. The size of this average period separation ($`40`$ s) is consistent with the expected mean period spacing of a normal-mass ($`0.6M_{\mathrm{}}`$) DBV white dwarf pulsating in $`\mathrm{}=1`$ modes (see, e.g. Bradley, Winget & Wood 1993).

A comparison of the individual mode periods of the known $`\mathrm{}=1`$ pulsator GD 358 (Winget et al. 1994, Vuille et al. 2000) and those of another DBV, CBS 114 (Handler et al. 2002), with that of PG 1654+160 also supports this interpretation. However, the number of available observed modes of PG 1654+160 is insufficient for seismic model calculations, and the uncertainties of their periods are too large.

What may be the cause of the amplitude (and possibly also frequency) variability in the two stars? As neither has been reported to be magnetic in the literature, interaction between the different pulsation modes remains the most promising hypothesis for an explanation.

In this case, the time scale of the amplitude variability is expected to be of the order of the inverse growth rates of the affected modes. Growth rates are not very well known for pulsating white dwarfs, but it is clear that longer-period modes have larger growth rates than shorter-period ones. Detailed growth-rate calculations (Dolez & Vauclair 1981) imply that amplitude variability may occur on time scales down to about one week.

These theoretical predictions are consistent with our observations, at least as far as we can tell. The longer-period modes of PG 1654+160 indeed seem to vary more rapidly in amplitude than the ones at shorter period (it is interesting to note that Kepler et al. (2002) made the same observation for GD 358), as implied by our attempts to trace these variations. The time scale of the amplitude variability of both stars also appears to be of the expected order of magnitude. However, we must admit that the temporal distribution of our data is such that we can only detect variations on just these time scales. Hence, the agreement we find can at best be regarded as qualitative.

## 5 Summary and conclusions

We have carried out new Whole Earth Telescope measurements of the two pulsating DB white dwarf stars KUV 05134+2605 and PG 1654+160 which were supplemented by single-site data. We also re-analysed all available archival measurements of the two stars.

We showed, for the first time, that both have rich pulsational mode spectra, and that the pulsation amplitudes of both stars are highly variable in time; PG 1654+160 may show some frequency variability in addition. Beating of multiple pulsation modes cannot explain all our observations, as the observed amplitude and frequency variability is too complex for such an interpretation; hence it must be intrinsic. The pronounced amplitude variations made it impossible to find stable modes to determine the evolutionary period change rates of the two stars.

Whereas there seems no systematic pattern in the periods of KUV 05134+2605 we measured, some of the modes of PG 1654+160 appear at the same periods whenever detected. The spacing of these periods, around 40 s, suggests that they are probably caused by non-radial gravity-mode pulsations of spherical degree $`\mathrm{}=1`$ in a normal-mass DBV white dwarf.

The amplitude variabilities of both stars could be followed by means of the pre- and post-WET observations that were therefore essential for this work. Their time scales are consistent with theoretical predictions of resonant mode coupling. This conclusion is however weakened by the temporal distribution of our data, which favour the detection of just those variability time scales.

Before a more detailed investigation of the amplitude variations of these two stars can be performed (e.g. to guide theoretical work in this direction, Buchler, Goupil & Serre 1995), mode identifications and an improved sampling of the temporal behaviour of the pulsations through continued single-site measurements are desirable. Given the qualitative similarity of PG 1654 and the “typical” DBV GD 358, we expect that the same nonlinear mode coupling and amplitude modulation mechanisms are at work in both stars. Having very rich mode spectra, both KUV 05134+2605 and PG 1654+160 are also attractive targets for future extensive multisite campaigns.

## ACKNOWLEDGEMENTS

We acknowledge support from Iowa State University, in part through NSF Grant AST-9876655. M. Cunha is supported through the grants PD/18893/98, of FCT-Portugal, and POCTI/1999/FIS/34549 approved by FCT and POCTI, with funds from the European Community programme FEDER. P. Moskalik acknowledges partial financial support by the Polish KBN grant 5 P03D 012 20.


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# Anti-shielding Effect and Negative Temperature in Instantaneously Reversed Electric Fields and Left-Handed Media

## I Introduction

This paper is concerned with the physically interesting anti-shielding effects of electric and magnetic dipoles, and the related phenomena such as the negative absolute temperature of dipole systems and the consequent superluminal light propagation. In nature, neither of the above three effects ( phenomena ) is easily observed. Although negative magnetic permeability has been shown to be possible when a polariton resonance exists in the permeability, such as in the antiferromagnets MnF2 and FeF2, or certain insulating ferromagnets, a negative permeability ($`\mu `$) with low losses coexisting with a negative electric permittivity ($`ϵ`$) has not been demonstrated. This means that in these magnetic anti-shielding materials ( $`\mu <0,ϵ>0`$ ), electromagnetic wave cannot propagate through it, since the negative magnetic permeability and positive electric permittivity may result in an imaginary index of refraction. The principal reason for the state of negative absolute temperature being rarely observed in nature lies in that the attainment of negative temperature should be restricted to some critical conditions such as that the system must possess an upper limit to the possible energy level of the allowed states; and the system should be thermally isolated from other system at positive temperature, for if a negative- and positive- temperature systems are in thermal contact, energy will be given up from the negative temperature to the positive, and therefore the negative-temperature system will decay to a normal state ( positive temperature ) through infinite temperature. In history, only the experiments of nuclear spin systems of some crystals, where the state of negative absolute temperature might be attained, were carried out.

What is referenced above is in connection only with the anti-shielding effect and negative temperature of magnetic media; the light propagation in electric and magnetic anti-shielding media is not involved in these investigations. Here, however, we take into account the anti-shielding effect of electric media and the light propagation inside it, i. e., we deal with the statistical mechanics of the state of negative temperature caused by the instantaneous reversal of the exterior electric field and, based on this, briefly discuss the negative effective rest mass term of light due to negative temperature and the consequent superluminality effect in the anti-shielding dielectric. Here the negative effective rest mass term of light means that the electromagnetic field propagating inside the anti-shielding medium would acquire an imaginary rest mass. Although it sounds somewhat surprising that in the anti-shielding dielectric there exists the superluminal light propagation, this superluminality motion associated with the particle velocity rather than with the group velocity of the light field is actually familiar to us, since it is in connection with the “ tachyon ” representation in the Poincar$`\stackrel{´}{\mathrm{e}}`$ group and is therefore said to be theoretically natural.

In the present paper, the potential fact that the negative absolute temperature of dipole systems of left-handed media is also demonstrated. Left-handed media is such a hypothetical material which has a simultaneously negative electric permittivity  and magnetic permeability. In 1968, Veselago predicted that electromagnetic plane wave in a left-handed medium would propagate in a direction opposite to that of the flow of energy. It is of interest that the refractive index, $`n`$, of this medium is also negative, which can be rigorously derived by analyzing the boundary conditions of incident waves on the interface between left-handed and ordinary media. This, therefore, means that on the interface between air and left-handed media, anomalous refraction takes place. It is apparently seen that in this media where both permittivity and permeability are taken to be negative, the anti-shielding effect arises.

We hold that there exists close relationship between the electromagnetic anti-shielding effect and the negative absolute temperature as well as the potential superluminal light propagation due to anti-shielding effects. The superluminal light propagation presented in this paper results from the statistical fluctuations of polarization charge in negative-temperature media, as will be discussed in Sec. 3. Since in the present paper we concern ourselves much with the light propagation in media, in next section we propose a phenomenological theory of effective rest mass term of light field, which is helpful in considering the light propagation in anti-shielding and negative-temperature media. The viewpoint of effective rest mass of electromagnetic field in media is useful in giving the vivid descriptions of some physical effects, for example, the Meissner effect in superconductivity can be interpreted as follows: the superconducting electrons, which produce the self-induced charge current, can provide the electromagnetic field with an effective rest mass ($`m_{eff}`$), and this nonvanishing $`m_{eff}`$ is therefore responsible for the fact that the magnetic field penetrates only a short distance ( proportional to $`m_{eff}^1`$ ) within the surface of a superconductor. The interaction of light wave with media is one of the leading subjects in classical electrodynamics and quantum optics, where a multitude of physical processes can often be phenomenologically described by useful models at classical and/or quantum level.

## II Effective rest mass term of light field

In history, possibility of a light pulse with speed greater than that ($`c`$) in a vacuum has been extensively investigated by many authors. The various experiments with microwave signals performed by Nimtz et al. revealed superluminal velocities of evanescent modes. Wang et al. used the method of gain-assisted linear anomalous dispersion to demonstrate the superluminal light propagation in the atomic caesium gas and measured a negative group-velocity index of the medium that means the faster-than-$`c`$ propagation of light. We suggest that, based on the theory of effective rest mass of light field, Wang’s superluminal propagation due to the anomalous dispersion in the gaseous atomic medium can be phenomenologically understood as follows:

The relation between the frequency $`\omega `$ and wave vector $`k`$ of lightwave propagating inside the dispersive medium may be $`\frac{\omega ^2}{k^2}=\frac{c^2}{n^2}`$ with $`n`$ being the optical refractive index. For highly absorptive media, the corresponding modification of this method can also apply. So, for convenience, here we are not ready to deal with the case of absorptive materials. This dispersion relation $`\frac{\omega ^2}{k^2}=\frac{c^2}{n^2}`$ yields

$$\frac{\omega ^2}{k^2}=\frac{c^2}{1\frac{c^4}{\mathrm{}^2}\frac{m^2}{\omega ^2}}$$
(1)
with the effective rest mass, $`m`$, of the light being so defined that $`m`$, $`n`$ and $`\omega `$ together satisfy the following relation

$$\frac{m^2c^4}{\mathrm{}^2}=(1n^2)\omega ^2.$$
(2)
This, therefore, implies that the particle velocity of light ( photons ) is $`v=nc`$ and the phase velocity of light is $`v_p=\frac{c}{n}=\frac{c^2}{v}`$. Since this relation is familiar to us, we thus show that the above calculation is self-consistent, at least for the de Broglie wave ( particle ).

As an illustrative example of the application of the above formulation, we now evaluate the effective rest mass of lightwave propagating in some certain media. For instance, we consider the case of electron plasma in which the relative permittivity $`ϵ(\omega )`$ reads

$$ϵ(\omega )=1\frac{\omega _p^2}{\omega ^2},\omega _p^2=\frac{N(e^{})^2}{mϵ_0}$$
(3)
with $`\omega _p,N,e^{},m`$ and $`ϵ_0`$ being the electron plasma frequency, number of electrons per unit volume, effective charge of electrons, electron mass and electric permittivity in a vacuum, respectively. Note that here the electron plasma is regarded as cold plasma where the thermal effects can be ignored. Since the relative magnetic permeability, $`\mu `$, of this plasma can be approximately taken to be $`1`$ and in consequence the refractive index $`n(\omega )=\sqrt{ϵ(\omega )}`$, it follows from (2) and (3) that the effective rest mass of the incident electromagnetic wave ( $`\omega >\omega _p`$ ) is of the form

$$m_{eff}=\frac{\mathrm{}\omega _p}{c^2},$$
(4)
which is independent of the frequency of the electromagnetic wave propagating inside this plasma. It is of interest that the effective $`ϵ(\omega )`$ of the array of long metallic wires (ALMWs) ( that is now used to manufacture the left-handed materials ) behaves as that of plasma, which means that in ALMWs media ( $`ϵ(\omega )=1\frac{\omega _0^2}{\omega ^2},\mu =1`$ ), the lightwave may also acquire an $`\omega `$\- independent effective rest mass. However, in most dielectric, e. g., the anomalous dispersive media where the permittivity $`ϵ(\omega )`$ cannot be taken to be the plasma type, the propagating lightwave may therefore acquire an $`\omega `$\- dependent effective rest mass. In what follows we calculate the group velocity in order to consider the superluminal light propagation in anomalous dispersive media.

It follows that the group-velocity index is

$$n_g=\frac{1}{n}\frac{mc^3}{\mathrm{}^2k}\frac{\mathrm{d}m}{\mathrm{d}\omega },$$
(5)
which can yield the familiar formula

$$n_g=n+\omega \frac{\mathrm{d}n}{\mathrm{d}\omega },$$
(6)
so long as we substitute the expression for the effective rest mass $`m`$ into the expression (5). Thus, the group velocity of light pulse is

$$v_g=\frac{c}{n_g}=\frac{nc}{1\frac{mnc^3}{\mathrm{}^2k}\frac{\mathrm{d}m}{\mathrm{d}\omega }}.$$
(7)
This, therefore, means that if the rest mass $`m`$ is independent of $`\omega `$, then the particle velocity $`v=nc`$ equals the group velocity $`v_g`$, which is analogous to the case of the de Broglie particle; nevertheless, if the effective rest mass $`m`$ of the light in the dispersive medium depends strongly on $`\omega `$ ( e. g., the property caused in the anomalous-dispersive medium ), then the group velocity $`v_g`$ is completely divorced from the particle velocity $`v`$ and may be greater than $`c`$ or even negative. Here both the particle velocity and the group velocity refer to those of the same matter wave that possesses the wave-particle duality. Note, however, that although the group velocity $`v_g`$ of light propagation exceeds $`c`$ of the speed of light in a vacuum, this superluminal phenomenon is not related closely to the special relativity since in this case the particle velocity of photons does not often necessarily exceed $`c`$. In the present paper, from the point of view of effective rest mass we suggest a new possible superluminality effect of light in the negative-temperature medium ( i. e., the dielectric placed in the instantaneously reversed electric fields ). Since it is connection with the particle velocity, rather than with the group velocity measured in Wang’s superluminal experiment, this superluminal light propagation in the present paper is related closely to the dynamics of special relativity, in other words, the particle velocity ( rather than the group velocity ) of light ( photons ) propagating through the state of negative temperature may exceed $`c`$ of the photon in a vacuum; the negative effective rest mass term of light results from the state of negative absolute temperature that is caused by the electric anti-shielding effect ( due to the instantaneous reversals of external electric fields ).

## III Anti-shielding effect of electric dipoles in state of negative temperature

The potential energy of the electric dipole moment $`p_0`$ in the exterior electric field $`E`$ is $`\epsilon _i=\frac{p_0D\mathrm{cos}\theta _i}{ϵϵ_0}`$, where $`ϵ`$ and $`ϵ_0`$ are respectively the relative permittivity of dielectric and the permittivity of free space; $`D`$ stands for the electric displacement vector. $`\theta _i`$ is taken to be in the region $`0\theta _i<\frac{\pi }{2}`$. We regard the continuous angle $`\theta `$ between dipole moment and exterior field as the discrete $`\theta _i`$ in order to simplify the following calculations. This means the index $`i`$ ranges from $`1`$ to $`\mathrm{}`$. Let $`N_i^+`$ and $`N_i^{}`$ respectively denote the occupation numbers of the electric dipoles with the potential energy $`\epsilon _i`$ and $`\epsilon _i`$. Thus the total number $`N`$ of electric dipoles in the dielectric medium and the total potential energy $`U`$ of these dipoles in exterior field are given as follows

$$N=\underset{i}{}\left(N_i^++N_i^{}\right),U=\underset{i}{}\left(N_i^+N_i^{}\right)\epsilon _i.$$
(8)
$`N_i^+`$ and $`N_i^{}`$ are solved in what follows. For convenience, we set $`N_i^+=\frac{1}{2}(a_i+b_i)`$ and $`N_i^{}=\frac{1}{2}(a_ib_i)`$, and then we have $`a_i=N_i^++N_i^{},b_i=N_i^+N_i^{}`$ and $`N=_ia_i,U=_ib_i\epsilon _i`$. It is apparent that $`N`$ can be rewritten

$$N=N\frac{_ic_i}{_jc_j}+\underset{i}{}f_i$$
(9)
with $`_if_i=0`$. Since $`N=_ia_i`$, it follows that $`a_i=N\frac{c_i}{_jc_j}+f_i`$.

In the similar fashion, $`U`$ can be rewritten

$$U=\frac{_id_i}{_jd_j}U+\underset{i}{}g_i\epsilon _i$$
(10)
with $`_ig_i\epsilon _i=0`$. Since $`U=_ib_i\epsilon _i`$, it follows that $`b_i\epsilon _i=\frac{d_i}{_jd_j}U+g_i\epsilon _i`$ or $`b_i=\frac{1}{_jd_j}\frac{d_i}{\epsilon _i}U+g_i`$.

Thus according to the above calculations, the general solution of Eqs. (8) is of the form

$$N_i^+=\frac{1}{2}\left(\frac{Nc_i}{_jc_j}+\frac{1}{_jd_j}\frac{d_i}{\epsilon _i}U+f_i+g_i\right),N_i^{}=\frac{1}{2}\left(\frac{Nc_i}{_jc_j}\frac{1}{_jd_j}\frac{d_i}{\epsilon _i}U+f_ig_i\right).$$
(11)
The parameters, $`c_i,`$ $`d_i,`$ $`f_i`$ and $`g_i`$, in the general solution (11) should be determined by using the physical conditions of the true distribution. It is readily verified that in the two-level system such as spin-$`\frac{1}{2}`$ model, the parameters $`c_i,d_i`$ and $`f_i,g_i`$ in the occupation numbers $`N_i^+`$ and $`N_i^{}`$ may be $`c_i=d_i=\epsilon _i`$ and $`f_i=g_i=0`$. Thus the form of $`N_i^+`$ and $`N_i^{}`$ is reduced to that of the familiar two-level system. This shows that the above calculations are self-consistent.

According to the Boltzmann’s entropy formula ( Boltzmann’s relation ), one has

$$S=k_B\mathrm{ln}\underset{i}{}\frac{N!}{N_i^+!N_i^{}}k_B[N\mathrm{ln}N\underset{i}{}\left(N_i^+\mathrm{ln}N_i^++N_i^{}\mathrm{ln}N_i^{}\right)].$$
(12)
By using $`\frac{}{U}\left(N_i^+\mathrm{ln}N_i^+\right)=\frac{1}{2}\frac{1}{_jd_j}\frac{d_i}{\epsilon _i}\left(\mathrm{ln}N_i^++1\right),\frac{}{U}\left(N_i^{}\mathrm{ln}N_i^{}\right)=\frac{1}{2}\frac{1}{_jd_j}\frac{d_i}{\epsilon _i}\left(\mathrm{ln}N_i^{}+1\right)`$, one can arrive at

$`{\displaystyle \frac{1}{T}}=({\displaystyle \frac{S}{U}})_D`$ $`=`$ $`{\displaystyle \frac{k_B}{2_jd_j}}{\displaystyle \underset{i}{}}{\displaystyle \frac{d_i}{\epsilon _i}}\mathrm{ln}{\displaystyle \frac{N_i^{}}{N_i^+}}`$ (13)
$`=`$ $`{\displaystyle \frac{k_B}{2_jd_j}}{\displaystyle \underset{i}{}}{\displaystyle \frac{d_i}{\epsilon _i}}\mathrm{ln}\left\{{\displaystyle \frac{\frac{Nc_i}{_jc_j}\frac{1}{_jd_j}\frac{d_i}{\epsilon _i}[_l(N_l^+N_l^{})\epsilon _l]+f_ig_i}{\frac{Nc_i}{_jc_j}+\frac{1}{_jd_j}\frac{d_i}{\epsilon _i}[_l(N_l^+N_l^{})\epsilon _l]+f_i+g_i}}\right\},`$ (14)
where $`D=ϵϵ_0E,\epsilon _i=\frac{1}{ϵϵ_0}p_0D\mathrm{cos}\theta _i`$. Here in our tentative analysis we only consider the isotropic homogeneous medium where the relation $`D=ϵϵ_0E`$ holds.

In the two-level system, both $`c_i`$ and $`d_i`$ are reduced to $`\epsilon _i`$. This, therefore, means that in general case, $`c_i`$ and $`d_i`$ may also be the odd functions of $`D`$ ( or the exterior electric field strength $`E`$ ). The reason lies in that when the instantaneous inversion of the exterior electric field $`E`$ takes place, some physical quantities will acquire a minus sign, i. e., $`EE,c_ic_i,d_id_i`$, but $`N_i^+`$ and $`N_i^{}`$ are unchanged. From the expressions (11), it follows that both $`f_i+g_i`$ and $`f_ig_i`$ ( or both $`f_i`$ and $`g_i`$ ) are the even functions with respect to $`D`$. By using these results, it is shown that the absolute temperature $`T`$ in the expression (14) is the odd function with respect to $`D`$. This result means that if $`EE`$, then $`TT`$, namely, the instantaneous inversion of the exterior electric field may cause the state of negative temperature, which is analogous to the case in nuclear spin system e. g., the nuclear spin system of the pure LiF crystal . It is therefore apparent that if the swiftly varying exterior electric field inverses all of a sudden and simultaneously the inversion of the dipole moments cannot catch up with the rapid reversal of the exterior electric field, then after it takes the relaxation time $`\tau _1`$ of the dipole-dipole thermal equilibrium depending on the interaction between the dipole moments in the exterior field, the electric-dipole system is therefore getting into the state of negative absolute temperature. If the relaxation time $`\tau _1\tau _2`$ with $`\tau _2`$ being the dipole-lattice relaxation time of the thermal equilibrium between dipoles and lattices , then this state of negative-temperature dipole system can be readily realized in experiments. Note that this effect via the instant reversals of electric fields can be considered the first anti-shielding effect that acts on the electric dipoles. Its essential feature is characterized by the fact that the total potential energy of dipole system in the reversed field is positive ( $`U>0`$ ). Here one may refer to the case of $`U<0`$ as the normal shielding effect in electromagnetic media.

It is verified that a second anti-shielding effect due to the state of negative temperature acting upon the electromagnetic wave occurs in the dielectric medium when the light is propagating through it. In general the light field will acquire an effective rest mass term resulting from the shielding effect of electric dipoles. In the case of the instantaneously reversed fields, this mass term in the field equation, however, possesses a minus sign caused by the negative temperature $`T`$. The equation of the electric field shielded by the electric dipoles may be given $`^2\mathrm{\Phi }=\frac{Q}{ϵ_0}\delta n`$ with $`Q`$ being the polarized effective charge in each electric dipole. The right-handed side of this equation arises from the polarization and shielding effect of electric dipoles and $`\delta n=n[1\mathrm{exp}(\frac{Q\mathrm{\Phi }}{k_BT})]`$, where $`n=n_0\frac{p_0E}{k_BT}[\mathrm{sinh}(\frac{p_0E}{k_BT})]^1`$ with $`n_0`$ denoting the volume density of the electric dipoles in the dielectric medium. We take the first-order approximation of $`\delta n`$ and arrive at the result $`\delta nn\frac{Q\mathrm{\Phi }}{k_BT}`$. Substitution of $`\delta n`$ into the above electric field equation yields

$$^2\mathrm{\Phi }\frac{nQ^2}{ϵ_0k_BT}\mathrm{\Phi }=0.$$
(15)
It follows that the negative effective rest mass term, $`\frac{nQ^2}{ϵ_0k_BT}\mathrm{\Phi }`$, in the field equation (15) of electric field arises from the anti-shielding effect of electric dipoles due to the state of negative temperature. Further calculation shows that the effective rest mass of light field propagating inside this dielectric may be expressed as

$$m_{eff}=\frac{\mathrm{}}{c}\left(\frac{nQ^2}{ϵ_0k_BT}\right)^{\frac{1}{2}}.$$
(16)
Hence we know that if the temperature, $`T`$, of the dipole system becomes negative, then the effective rest mass ( that accordingly becomes an imaginary number ) of light field may lead to the superluminal light propagation in dielectric media. In the state of low temperature, e. g., $`T=1\mathrm{K}`$, if the instantaneous inversion of the exterior electric field takes place, then the order of magnitude of $`\left|m_{eff}\right|`$ may be $`10^{31}\mathrm{kg}`$, where without loss of generality $`Q`$ and $`n`$ are taken to be $`10^{20}\mathrm{C}`$ and $`10^{28}/\mathrm{m}^3`$, respectively. This means that once the typical light propagation with $`\mathrm{}\omega =10^{19}\mathrm{J}`$ approaches the dielectric medium in the state of negative temperature, the light field obtains a negative rest mass term and therefore will exceed $`c`$. The similar effect occurs when the supersymmetric partner of the photon, i. e., photinos ( should such exist ) propagates in this anti-shielding dielectric medium and will obtain a negative effective rest mass, which results in the possible negative speed ( $`𝐯<0`$ ) against the propagation direction. It is of interest that the negative speed is faster than the speed exceeding $`c`$ ( even faster than the positively infinite velocity ), just similar to the fact that the state of negative temperature is hotter than that of positively infinite temperature. In addition, it should be noted that the potential superluminal light propagation in the state of negative temperature ( or the anti-shielding dielectric ) is not at odds with the special relativity nor does it violate the principle of causality, since the above theoretical analysis concerning the superluminal effect is a direct consequence of both the Maxwell’s theory and the dynamics of the special relativity. Moreover, this superluminal propagation with particle velocity exceeding $`c`$ is not strange to us, since there also exists the “ tachyon ” representation with the four-dimensional momentum squared $`p^\mu p_\mu <0`$ in the Poincar$`\stackrel{´}{\mathrm{e}}`$ group, so that this superluminal motion discussed above is natural from the theoretical point of view. We hold that it deserved the experimental investigation.

How to measure the velocity of this superluminal light propagation in experiment? At low temperature, e. g., $`T=1\mathrm{K},`$ of the dielectric such as the crystals of HCl and HF, which each dipole respectively possesses $`3.62\times 10^{30}\mathrm{C}\mathrm{m}`$ and $`6.40\times 10^{30}\mathrm{C}\mathrm{m}`$ of the dipole moment, in the presence of exterior strong electric field that makes the electric dipoles polarized, the instantaneous reversal of the exterior field may cause the medium into the state of negative temperature. In this situation one may let a light pulse produced at $`t=0`$ propagate a distance $`l_1`$ and then go through such polarized medium with thickness $`l_2`$. If the light approaches the detector at $`t=t_1`$, then one may take $`v=\frac{cl_2}{ct_1l_{1\text{ }}}`$ , which exceeds $`c`$. It is worthwhile to point out that in this superluminal phenomenon the group velocity of light field made up of the photons equals the particle velocity of the photons, since the effective rest mass $`m_{eff}=\frac{\mathrm{}}{c}\left(\frac{nQ^2}{ϵ_0k_BT}\right)^{\frac{1}{2}}`$ is independent of the frequency $`\omega `$ of light field. This, therefore, implies that the group velocity of the light pulse propagating in the anti-shielding dielectric medium may also exceed $`c`$ .

To close this section we briefly consider the anti-shielding effect of thermal electron plasma. According to the Debye’s shielding effect, the Debye’s length is expressed by $`\lambda _D=\left(\frac{ϵ_0k_BT}{N(e^{})^2}\right)^{\frac{1}{2}}`$ with $`N`$ being the electron number in per unit volume; hence, the effective rest mass of light field due to this shielding effect is $`m_1=\frac{\mathrm{}}{c}\left(\frac{N(e^{})^2}{ϵ_0k_BT}\right)^{\frac{1}{2}}`$. If, for example, the plasma is placed in an exterior electric field, here the temperature $`T`$ in the expression for $`m_1`$ is that of the thermal equilibrium caused by potential-potential interaction between electrons themselves ( and ions ) in the electric field, where the particle distribution is in the real space ( associated with the electric potential $`\varphi \left(𝐱\right)`$ given by exterior field ), rather than in the velocity space ( associated with the Maxwell’s distribution law ). As is presented previously, in cold plasma the light field acquires an effective rest mass whose square is $`m_2^2=\frac{\mathrm{}^2}{c^2}\frac{N(e^{})^2}{ϵ_0}\frac{1}{mc^2}`$. This result can also apply to the thermal plasma. It thus follows that in thermal electron plasma the total square of rest mass of light field is written in the form

$$m_{total}^2=m_1^2+m_2^2=\frac{\mathrm{}^2}{c^2}\frac{N(e^{})^2}{ϵ_0}\left(\frac{1}{k_BT}+\frac{1}{mc^2}\right),$$
(17)
where $`T`$ is the temperature of electrons in potential-potential thermal equilibrium in the real space ( configuration space ). In general this temperature differs from the Maxwell’s temperature that depends upon the distribution of particle velocity ( in velocity space ). This thermal equilibrium ( Maxwell’s velocity distribution ) is often attained by, for instance, the electron-ion collisions where the relaxation time is proportional to $`N^1`$. This relaxation process to thermal equilibrium can be described by a kinetic equation. Once if the potential-potential relaxation time ( proportional to $`N^{\frac{1}{3}}`$ ) is far less than the electron-ion relaxation time, then in the process of the instantaneous reversal of exterior electric field, the potential-potential system is therefore thermally isolated from the Maxwell’s velocity distribution system. It follows from (17) that if the negative temperature $`T`$ caused by the instantaneous reversal of exterior field satisfies $`0^{}>T>\frac{mc^2}{k_B}`$, then the total effective mass squared $`m_{total}^2<0`$. However, it should be noted that in the case of thermal plasma the negative temperature is not easily achieved, since the potential-potential system consisting of both quasi-free electrons and ions possesses excessive free energy due to the stored positive potential energy of charged particles in reversed electric field and is therefore not very stable. Only a rather weak perturbation would necessarily destroy this negative-temperature system. For this reason we are therefore not interested in further considering the anti-shielding effect of thermal plasma and the related phenomena.

## IV Anti-shielding effect and negative temperature in left-handed media

More recently, a kind of composite media ( the so-called left-handed media ) having a frequency band where the effective permittivity ( $`\epsilon `$ ) and the effective permeability ( $`\mu `$ ) are simultaneously negative attracts attentions of many researchers in various fields such as materials science, condensed matter physics, optics and electromagnetism. Veselago first considered this peculiar medium and showed that it possesses a negative index of refraction. It follows from the Maxwell’s equations that in this medium the Poynting vector and wave vector of electromagnetic wave would be antiparallel, i. e., the vector k, the electric field E and the magnetic field H form a left-handed system; thus Veselago referred to such materials as “left-handed”, and correspondingly, the ordinary medium in which k, E and H form a right-handed system may be termed the “right-handed” medium. Other authors call this class of materials “negative-index media (NIM)”, “double negative media (DNM) ” and Veselago’s media. It is readily verified that in such media having both $`\epsilon `$ and $`\mu `$ negative, there exist a number of peculiar electromagnetic properties, for instance, many dramatically different propagation characteristics stem from the sign change of the group velocity, including reversal of both the Doppler shift and Cherenkov radiation, anomalous refraction, modified spontaneous emission rates and even reversals of radiation pressure to radiation tension. In experiments, this artificial negative electric permittivity media may be obtained by using the array of long metallic wires (ALMWs), which simulates the plasma behavior at microwave frequencies, and the artificial negative magnetic permeability media may be built up by using small resonant metallic particles, e. g., the split ring resonators (SRRs), with very high magnetic polarizability.

In linear media the electric and magnetic polarizations ( per unit volume ) is respectively

$$𝐏=(ϵ1)ϵ_0𝐄,𝐌=(\mu 1)𝐇.$$
(18)
The potential energy density of electric and magnetic dipoles in electromagnetic fields reads

$$U_e=𝐏𝐄=(ϵ1)ϵ_0𝐄^2,U_m=\mu _0𝐌𝐇=(\mu 1)\mu _0𝐇^2$$
(19)
with $`\mu _0`$ being the permeability of free space. It is apparent that in left-handed media where both $`ϵ`$ and $`\mu `$ are negative, the electric and magnetic polarizations, $`𝐏`$ and $`𝐌`$, are opposite to the electric and magnetic fields, $`𝐄`$ and $`𝐇`$, thus in general, the potential energy density, both $`U_e`$ and $`U_m`$, are positive, which differs from the cases in the conventional media, i. e., the right-handed media. This, therefore, means that left-handed media possess the anti-shielding effect, which results in many anomalous electromagnetic and optical behaviors, as is mentioned above.

May the electric and magnetic dipole systems be brought into the state of negative absolute temperature when the electromagnetic wave is propagating in left-handed media? We show that under some restricted conditions, these dipole systems may possess a negative temperature indeed. The detailed analysis is given in what follows:

According to Ramsey’s claim that the essential requirement for a thermodynamical system to be capable of a negative temperature is that the elements of the thermodynamical system must be in thermodynamical equilibrium among themselves in order that the system can be described by a temperature at all. For the left-handed media, this may be understood in the sense: the electric and magnetic dipole moments produced by ALMWs and SRRs should be coupled respectively to each other, and this dipole-dipole interactions must be strong and therefore the thermodynamical equilibriums between themselves may be brought about in a short time, which is characterized by the relaxation time $`\tau _1`$. But here both ALMWs and SRRs are macroscopic elements of left-handed medium ( e. g., the length scale of SRRs is mm ), which implies that there exists a problem as to whether the concept of thermodynamical equilibrium is applicable to these macroscopic elements or not. This problem, however, is not the subject of this section, and it will be published in a separate paper; furthermore, if, for example, we can find a kind of molecular-type SRRs ( i. e., the C- or $`\mathrm{\Omega }`$\- like curved organic molecule that possesses the delocalized $`\pi `$ bond and can therefore provide a molecular electric current induced by magnetic field of lightwave ) for manufacturing the left-handed media, then the dipole system of this media can be appropriately described by a temperature. So in our tentative consideration in this paper, we can study the anti-shielding effect and negative temperature of left-handed media from the phenomenological point of view, ignoring the detailed information about the elemental atoms which constitute the left-handed media.

In order to generate a state of negative absolute temperature, the following requirement for a thermodynamical system should also be satisfied: the system must be thermally isolated from all other systems, namely, the thermal equilibrium time ($`\tau _1`$) among the elements of the negative-temperature system must be short compared to the time during which appreciable energy is lost to or gained from other systems. In left-handed media, the dipole-lattice interaction causes heat to flow from the dipole system ( negative temperature ) to the lattice system ( positive temperature ). If the relaxation time ($`\tau _2`$) during which this interaction brings the dipole-lattice system into thermodynamical equilibrium is much greater than $`\tau _1,`$ then it may be said that the dipole system is thermally isolated from the lattice system, and the dipole system is therefore capable of a negative temperature. In addition to this condition, there exists another restriction, i. e., the state of negative temperature should be built up within half period of electromagnetic wave propagating inside the left-handed medium, i. e., the relaxation time $`\tau _1`$ should be much less than $`\frac{1}{f}`$ with $`f`$ being the frequency of electromagnetic wave, which means that this thermodynamical process caused by dipole-wave interaction can be considered a quasi-stationary process and in consequence the state of negative temperature of dipole system due to dipole-dipole interaction may adiabatically achieve establishment in every instantaneous interval during one period of electromagnetic wave. If this condition is not satisfied, say, the relaxation time $`\tau _1`$ is several times as long as $`\frac{1}{f}`$, then the negative temperature of dipole systems cannot be achieved since the thermodynamical equilibrium among dipoles induced by the oscillating electromagnetic fields $`𝐄`$ and $`𝐇`$ may lose its possibility, namely, the concept of thermodynamical equilibrium is not applicable to this non-stationary process; in fact, it should be treated by using non-equilibrium statistical mechanics. In view of above discussions, we conclude that the principal conditions for the electric and magnetic dipole systems of left-handed media possessing a negative temperature may be ascribed to the following two essential requirements

$$\tau _1\tau _2,\tau _1\frac{1}{f}.$$
(20)
Generally speaking, the first restriction, $`\tau _1\tau _2`$, is readily achieved, since in electromagnetic media the dipole-dipole interaction are often much stronger than the dipole-lattice interaction. For example, in some nuclear spin systems such as the pure crystal of LiF where the negative temperature was first realized in experiments, the relaxation time $`\tau _1`$ of spin-spin process is approximately the period of the Larmor precession of one nucleus in the field of its neighbor and is of the order of $`10^5`$ second while the relaxation time that depends strongly upon the interaction between the spin system and the crystal lattice is several minutes. In the recent work of designing the structures of more effective left-handed media, use is made of the SRRs of high electromagnetic polarizability. This leads to the very strong dipole-dipole interaction and may achieve the thermodynamical equilibrium of dipole system with shorter relaxation time. If this interaction is rather strong and therefore agrees with the second restriction, $`\tau _1\frac{1}{f}`$ with $`f`$ being in the region of GHz, then the dipole systems of left-handed media may be said to be in the state of negative absolute temperature.

Since the most conspicuous feature of left-handed media may be the electromagnetic anti-shielding effect, the previous considerations concerning the superluminal light propagation in the instantly varying electric fields based on the viewpoint of effective rest mass can also be applied to the incident electromagnetic wave propagating inside left-handed media. As is stated, in left-handed media many electromagnetic effects such as Doppler shift, Cherenkov radiation and wave refraction are inverted compared with those in ordinary right-handed media. In the similar fashion, it is believed that this superluminal light propagation may also probably occur in left-handed media. Moreover, in some electromagnetic materials, there exists another superluminal pulse propagation that also results from the anti-shielding effect ( but rather than from the statistical fluctuations in negative temperature ), since in this media the designed equivalent permittivity and permeability based on the so-called two-time-derivative Lorentz model are simultaneously smaller than the values in free space. Ziolkowski has studied the superluminal pulse propagation and consequent superluminal information exchange in this media, and demonstrated that they do not violate the principle of causality. We suggest that all these potential superluminality effects of light propagation in anti-shielding media should be further investigated, particularly in experiments.

## V Concluding remarks

In electromagnetic systems, the anti-shielding effect is not easily found. The normal shielding effect makes the speed of light wave propagating inside media less than that in a vacuum. In these media the directions of induced electric and magnetic dipoles are parallel ( not antiparallel ) to the electromagnetic fields, and hence the potential energy of these dipoles in the fields are negative as is stated in (19). It is for these reasons that in electromagnetic media, systems of negative temperature occur only rarely. In the present paper, for the case of the instantaneous reversal of exterior electric field, we take into consideration the state of negative temperature and the anti-shielding effect of electric dipoles. It follows that if the energy $`\epsilon _i`$ is changed into $`\epsilon _i`$, i. e., once the external field strength changes the sign, after taking the relaxation time the temperature might accordingly become negative ( additionally, in the meanwhile the restriction of the dipole-dipole relaxation time being much shorter than the dipole-lattice relaxation time should also be satisfied ). Meanwhile, it follows from the expression for the effective rest mass $`m_{eff}=\frac{\mathrm{}}{c}\left(\frac{nQ^2}{ϵ_0k_BT}\right)^{\frac{1}{2}}`$ that if $`TT`$, then $`m_{eff}`$ may become imaginary. Hence it is shown from the point of view of effective rest mass that the potentially interesting superluminal light propagation in media may result from this anti-shielding effect of dielectric in the state of negative temperature. According to the conventional viewpoints, the “ tachyon ” representation in the Poincar$`\stackrel{´}{\mathrm{e}}`$ group is often considered the non-physical representation. On the contrary, however, we favor that probably in some certain anti-shielding cases ( including the negative-temperature state ), this potential superluminal propagation of light would exist, which deserves the further investigation.

For the case of left-handed media, the anti-shielding effect and the requirements for left-handed media to be capable of negative temperature is analyzed in this paper. In recent investigations regarding the manufacture of left-handed materials, the media capable of negative index of refraction is restricted to the microwave frequency region, since the resonance frequency of SRRs ( and ALMWs ) is low (GHz). If one can find the molecular-type SRRs by certain artificial molecule arrangements, which has the conjugation effect of organic molecules due to the delocalized $`\pi `$ bond and the consequent high magnetic susceptibility, then the resonance frequency would be readily raised greatly by several orders of magnitude. Based on this, it is of physical significance to consider the interaction of radiation fields with negative-temperature systems in left-handed media. Klimov theoretically studied the processes of spontaneous emission of an atom placed near a body ( sphere ) made of the Left-handed material and placed in the right-handed medium, and showed that these processes drastically differ from those near usual right-handed body. We think if the statistical effect ( including negative temperature ) of left-handed is taken into account, then the results obtained by Klimov should be modified. This modification is under consideration based on the combination of Klimov’s formulation and the thermodynamics and statistical mechanics.

Acknowledgements The author thanks Q. Wu, T. Chang and X. M. Wu for their beneficial discussions concerning the superluminal light propagation. I have benefited from useful criticism and advice from C. Alden Mead. My special thanks are due to him also. This project is supported in part by the National Natural Science Foundation of China under the project No. $`90101024`$.


text:
# Origins of Chevron Rollovers in Non-Two-State Protein Folding Kinetics

## Abstract

Chevron rollovers of some proteins imply that their logarithmic folding rates are nonlinear in native stability. This is predicted by lattice and continuum Gō models to arise from diminished accessibilities of the ground state from transiently populated compact conformations under strongly native conditions. Despite these models’ native-centric interactions, the slowdown is due partly to kinetic trapping caused by some of the folding intermediates’ nonnative topologies. Notably, simple two-state folding kinetics of small single-domain proteins are not reproduced by common Gō-like schemes.

PACS Numbers: 87.15.Aa, 87.15.Cc, 87.15.He, 87.15.By

The physical basis of protein folding is a central unresolved puzzle in molecular biology. Recently, much advance in protein folding has originated from experiments on small single-domain proteins  with simple two-state folding and unfolding kinetics typified by that of CI2 , with features including: (i) single-exponential relaxation, (ii) the logarithmic folding and unfolding rates ($`\mathrm{ln}k_\mathrm{f}`$ and $`\mathrm{ln}k_\mathrm{u}`$) at constant temperature being essentially linear in chemical denaturant (urea or GuHCl) concentration, i.e., both arms of the “chevron plot”  are linear, and that (iii) the equilibrium ratio of native to denatured conformational population $`K`$ \[native\]/\[denatured\] $`=k_\mathrm{f}/k_\mathrm{u}`$. What form of intrachain interactions might give rise to such remarkable behavior is a question of fundamental biophysical interest.

Other proteins’ corresponding properties are more complex. Often this is manifested by significant deviations \[4–9\] from the above linearities, i.e., they exhibit chevron rollovers . We refer to their kinetics as non-two-state. Examples of such behavior include barnase , ribonuclease A , hen lysozyme , and U1A . The present operational definition of non-two-state kinetics encompasses what some authors called “two-state” (though not “simple”) when conditions (i) and (iii) above are satisfied but not (ii) . Chevron rollover can also be brought about by mutation, as in S6  and BPTI . Thus, rather than an aberration, chevron rollover is quite ubiquitous. Therefore, ascertaining its physical origins should provide important clues to protein energetics.

Chevron rollovers have been attributed to peculiarities of intermediates or transition states on postulated free energy profiles \[4–8,10\], or front factors’ sensitivity to folding conditions . Yet these phenomenological considerations do not pinpoint the physical processes involved. In this Letter, physical mechanisms underlying chevron rollovers are addressed directly by examining a multitude of trajectories from several protein chain models.

The recent discovery of a remarkable correlation between contact order and folding rates of simple two-state proteins  has led to extensive studies of Gō-like protein models \[13–17\]. Hence, a natural question is whether common Gō-like constructs do predict simple two-state kinetics. Somewhat surprisingly, our investigation thus far indicates that this may not be the case. Instead, chevron rollover emerges as a conspicuous feature in both lattice  and continuum  Gō models. This suggests that common native-centric  chain constructs can be useful for elucidating the polymer mechanisms of chevron rollovers, even though they may not be entirely adequate for simple two-state proteins. Pursuing this logic, we now analyze a thermodynamically cooperative  48mer three-dimensional lattice Gō model . This model had notable impact on recent appraisals  of the energy landscape views of protein folding , but its chevron behavior has not been investigated.

Each native contact in this model has a favorable energy $`ϵ`$ ($`<0`$), nonnative contacts have zero energy. Folding/unfolding kinetics are modeled by Metropolis Monte Carlo (MC) dynamics with the same set of elementary chain moves as in : End moves are attempted for the two chain-end monomers. Corner and crankshaft moves are attempted for other monomers with 70% and 30% probability respectively. Time is measured by the number of attempted MC moves; $`Q`$ is fractional number of native contacts .

The chevron plots for this Gō model and a closely related model are shown in Fig. 1. When relaxation is single-exponential (see below), $`k_\mathrm{f}`$ or $`k_\mathrm{u}`$ $`=`$ 1/MFPT. Most of the MFPTs here are averaged from at least 1,000 trajectories, except for a narrow $`ϵ/k_\mathrm{B}T`$ range around the transition midpoint where kinetics are relatively slow (100–200 trajectories each) and for folding initiated from Fig. 2(d) (200 trajectories each). In these models, the free energy $`\mathrm{\Delta }G_\mathrm{u}`$ of unfolding to the open conformations ($`Q6/57`$) is essentially linear in $`ϵ/k_\mathrm{B}T`$. Thus we model denaturant concentration changes by varying $`ϵ/k_\mathrm{B}T`$ . Adding repulsive nonnative contact energies to a Gō model  does not appear to have a significant impact on the chevron behavior. Fig. 1 shows dramatic chevron rollovers of the folding arms and very slight rollovers of the unfolding arms for both models, with maximum folding rates at $`\mathrm{\Delta }G_\mathrm{u}/k_\mathrm{B}T`$= 14.2 (Gō) and 16.2 (Gō plus repulsion). Fig. 1 indicates that deviations from simple two-state behavior can be difficult to discern under weakly native conditions . To facilitate comparison with experiments, we characterize folding rollover by the difference between the hypothetical simple two-state $`\mathrm{ln}k_\mathrm{f}^{2\mathrm{s}}`$ (inclined dotted lines in Fig. 1) and the actual (simulated) folding rate $`\mathrm{ln}k_\mathrm{f}`$ $``$ $`\mathrm{ln}(\mathrm{MFPT})`$ at three representative values of native stability $`\mathrm{\Delta }G_\mathrm{u}`$, spanning a range typically covered by real proteins. Here, for $`\mathrm{\Delta }G_\mathrm{u}/k_\mathrm{B}T=`$ (5, 10, 15), the logarithmic rollover ratio $`\mathrm{ln}(k_\mathrm{f}^{2\mathrm{s}}/k_\mathrm{f})`$ $`=`$ ($`0.16`$, $`1.08`$, $`2.96`$) for the Gō model and ($`0.32`$, $`1.36`$, $`3.12`$) for the model with repulsive interactions. These ratios are not dissimilar to the corresponding $`\mathrm{ln}(k_\mathrm{f}^{2\mathrm{s}}/k_\mathrm{f})`$ $``$ ($`0.77`$, $`2.42`$, $`4.28`$) for wildtype barnase at 25C and pH 6.3 . Under these conditions, a maximum folding rate was not observed for barnase . However, if a quadratic dependence  of $`\mathrm{ln}k_\mathrm{f}`$ vs. denaturant is assumed for barnase (c.f. ), a maximum folding rate $`230`$ s-1 may be extrapolated to occur at an hypothetical $`\mathrm{\Delta }G_\mathrm{u}40k_\mathrm{B}T`$ which is much more stable than the $`\mathrm{\Delta }G_\mathrm{u}18.0k_\mathrm{B}T`$ at zero denaturant.

Fig. 2(a) provides the Gō model’s conformational distributions at different native stabilities. Under mildly native conditions ($`\mathrm{\Delta }G_\mathrm{u}<10k_\mathrm{B}T`$), the free energy profiles have a barrier between the native and denatured minima. Under more strongly native conditions ($`\mathrm{\Delta }G_\mathrm{u}>15k_\mathrm{B}T`$), their shapes are suggestive of downhill folding . The analysis of first passage time distribution  in Fig. 2(b) indicates that folding kinetics is approximately single exponential \[$`\mathrm{ln}P(t)`$ linear in $`t`$\] under mildly native conditions, consistent with the observed single-exponential folding kinetics for ribonuclease A when double-jump experiments were used to eliminate the effect of cis/trans proline isomerization . The behavior of wildtype barnase is similar: Folding is fast and single-exponential for the majority of the chains ($`80\%`$), the rest belongs to a slow-folding tail caused by proline isomerization . However, when modeling conditions are strongly native (corresponding conditions may not always be experimentally achievable ), folding kinetics is not single-exponential \[circles and squares in Fig. 2(b)\]. The onset of this behavior occurs approximately when the $`\mathrm{ln}[P(Q)]`$ profile becomes downhill and where folding rate is maximum (c.f. Figs. 1 and 2) . It would be instructive to ascertain whether this specific model prediction applies to real proteins.

A closer examination of the model folding trajectories indicates that the slowdown leading to folding-arm chevron rolloves arises from transiently populated compact non-ground-state conformations because these folding “intermediates” have lifetimes that increase with increasingly native conditions (Figs. 1, 3 and 4). Examples are shown in Fig. 3(b–d). Once one of these structures is adopted under strongly native conditions ($`ϵ/k_\mathrm{B}T>1.55`$), it takes longer on average to reach the ground state if intrachain native contacts are more favorable (Fig. 1). Folding trajectories under strongly native conditions are qualitatively different from that under milder conditions \[Fig. 4(a–c)\]. At the transition midpoint \[Fig. 4(c)\], interconversions between $`Q0.2`$ and $`Q1.0`$ are sudden and sharp. Relatively little time is spent at intermediate $`Q`$ values. As $`ϵ/k_\mathrm{B}T`$ increases, however, certain conformations with intermediate $`Q`$ $`0.6`$$`0.8`$ are frequented more. Even under mildly native conditions, their impeding effects on folding kinetics is already apparent from the event in Fig. 4(b) depicting the chain bounces back to $`Q0.2`$ after achieving $`Q0.8`$. But the lifetimes of these “intermediates” are brief compared to that of the open unfolded conformations. Hence folding remains approximately single-exponential \[triangles in Fig. 2(b)\]. However, when conditions become more strongly native \[Fig. 4(a)\], some folding trajectories are dominated by “intermediates,” leading to a significant reduction in average folding time. But even under these circumstances it is still possible to fold quickly \[Fig. 4(a), inset\]. Consistent with Fig. 2b (circles), this separation of time scales means that folding is no longer single-exponential.

In contrast to a previous report that no “entangled misfolded state” was observed during the folding of this particular Gō model , Fig. 3(b) exhibits an overall nonnative topology. For Fig. 3(c), the left side of the conformation is native, but the right side is substantially nonnative. Hence these conformations are kinetic traps in that they cannot reach the ground state without first open up somewhat by breaking some existing favorable contacts. Notwithstanding possible artifacts of lattice models \[Fig. 3(d)\], this basic physical requirement rationalizes folding-arm chevron rollover because favorable contacts contributing to the meta-stability of these traps are increasing difficult to break with stronger $`ϵ/k_\mathrm{B}T`$.

This prediction appears to be robust over a range of lattice and continuum coarse-grained models \[Fig. 4(d–e)\] that exhibit chevron rollovers. Fig. 4(d) shows that folding of a recent lattice model with residue-based as well as native-centric interactions are similar to that in Fig. 4(b). Fig. 4(e) shows that folding of a continuum Cα model under mildly and strongly \[inset in (e)\] native conditions are very much similar, respectively, to the corresponding lattice results in Fig. 4(b) and (a). The trajectories in Fig. 4(f) from a continuum model  with desolvation barriers  also show that intermediate $`Q`$ values are more prominent during the folding process when conditions are more strongly native \[inset in (f)\].

A maximum (or “optimal”) folding rate similar to those in Fig. 1 have been observed in many models (e.g., ) since it was first noted in HP model simulations more than a decade ago . This feature arises from a competition between a stronger driving force for folding and the onset of glassy dynamics under strongly native conditions (see note added in proof of ). However, until recently , the connection between this theoretical phenomenon and chevron rollover has not been recognized. Perhaps this is because the maximum folding rate often occurs near the transition midpoint for less cooperative models, and hence its relationship with chevron plots is less obvious. In contrast, the models studied here possess proteinlike thermodynamic cooperativity . Several basic principles now emerge: (i) Rollovers can arise from kinetic trapping ; but folding relaxation remains approximately single exponential when trapping effects are mild \[Fig. 2(b)\]. (ii) We have rationalized rollovers phenomenologically by front factors that depend on $`\mathrm{\Delta }G_\mathrm{u}`$ . Physically, this dependence is likely caused by trapping and unfolding (barrier recrossing) from transiently populated compact non-ground-state conformations (Fig. 4). These predictions are testable by experiments. (iii) The chevron rollovers in the Gō models presented suggest strongly that, contrary to expectation, Gō-like pairwise additive interactions are insufficient  to capture the remarkable kinetics of small single-domain proteins ; further research is necessary to ascertain the physical origin of their simple two-state cooperativity.

The authors thank Walid Houry for a very helpful discussion. This work was supported in part by Canadian Institute of Health Research grant MOP-15323.

Fig. 1 MFPT is mean first passage time, $`k_\mathrm{B}T`$ is Boltzmann constant times absolute temperature. Circles are for the 48mer Gō model . Squares are data from a model with the same ground-state conformation and attractive energy $`ϵ`$ for each native contact but with an additional repulsive energy $`ϵ`$ for each nonnative contact (as in the HP+ model  and Ref. ). Folding (open symbols) starts from a random self-avoiding walk, first passage is achieved when $`Q=1`$. Unfolding (filled symbols) starts from the $`Q=1`$ ground state, first passage is achieved when $`Q6/57`$ because the free energy minimum of the denatured states is at $`Q6/57`$. Solid dashed curves are mere guide for the eye. The vertical dotted lines mark the two model’s thermodynamic transition midpoints. The two pairs of V-shape dotted lines are hypothetical simple two-state chevron plots  based upon $`\mathrm{\Delta }G_\mathrm{u}`$ between $`Q=1`$ and $`Q6/57`$ obtained by histogram techniques from sampling around the transition midpoint. The triangles, asterisks, and diamonds are $`\mathrm{ln}(\mathrm{MFPT})`$ values for Gō-model folding initiated (at $`t=0`$) respectively from the compact conformations (b), (c), and (d) in Fig. 3. Arrows indicate the $`ϵ/k_\mathrm{B}T`$ values considered in Fig. 2.

Fig. 2 (a) Free energy profiles for the Gō model at the $`ϵ/k_\mathrm{B}T`$ values indicated (c.f. Fig. 1). $`P(Q)`$ is Boltzmann population distribution over $`Q`$. \[Note that $`P(Q)=0`$ for $`Q=`$ $`55/57`$ and $`56/57`$.\] (b) $`P(t)\mathrm{\Delta }t`$ is the fraction of folding trajectories with $`t\mathrm{\Delta }t/2<`$ first passage time $`t+\mathrm{\Delta }t/2`$ , plotted in different horizontal scales for different $`ϵ/k_\mathrm{B}T`$s \[symbols as in (a)\] to enhance clarity. For $`ϵ/k_\mathrm{B}T=`$ $`1.82`$, $`1.61`$, $`1.47`$, and $`1.28`$ respectively, 2,500, 2,030, 3,500, and 1,100 trajectories are analyzed using $`\mathrm{\Delta }t/10^6=`$ $`30`$, $`1.8`$, $`1.6`$, and $`30`$; the $`\mathrm{ln}[P(t)\mathrm{\Delta }t]`$ shown are for $`t`$ values equal to $`1`$, $`1/10`$, $`1/20`$, and $`1/2`$ of that given by the horizontal axis. Solid and dashed lines are linear fits for $`ϵ/k_\mathrm{B}T=`$ $`1.47`$ and $`1.28`$.

Fig. 3 (a) Ground state of the Gō model. (b–d) Transiently trapped conformations under strongly native conditions (c.f. Fig. 1), with $`Q=39/57`$, $`41/57`$ and $`53/57`$ respectively. The dotted, dashed, dotted-dashed lines and filled circles are used to identify monomers (in all four conformations) that belong to three of the straight edges and the core positions in the ground-state conformation (a). The conformation in (d) may reach the ground state by a simple hinge motion of the dotted-dashed edge. However, since such a move is not available in the model , the chain now must first partially open up before it can access the ground state. The trapping effect of (d) is minor compared to that of (b) and (c) (see Fig. 1).

Fig. 4 (a–c) Folding trajectories of the 48mer Gō model at $`ϵ/k_\mathrm{B}T=`$ $`1.82`$ (a), $`1.47`$ (b), and $`1.28`$ (c). The insets in (a, b) each shows a faster folding trajectories at the same given $`ϵ/k_\mathrm{B}T`$. (d–f) Typical folding trajectories in other models for comparison: (d) is from a 55mer lattice model under mildly native conditions ($`ϵ/k_\mathrm{B}T=1.75`$) . (e, f) are from the continuum NCS1 without-solvation (e) and with-solvation (f) Langevin dynamics models at $`T=0.82`$ for CI2  with $`ϵ=`$ $`0.88`$ (e) and $`1.1`$ (f). The insets in (e, f) show trajectories at the same $`T`$ but under more strongly native conditions at $`ϵ=`$ $`1.0`$ (e) and $`1.5`$ (f).


text:
# Deviation from the Kadowaki-Woods relation in Yb-based intermediate-valent systems

## 1 Introduction

The low-temperature properties of many U- and Ce-based intermetallic compounds are well described by Fermi-liquid state . Here, the specific heat $`C`$ and the electrical resistivity $`\rho `$ as a function of temperature $`T`$ vary as $`C\gamma T`$ and $`\rho AT^2`$, where $`\gamma `$ and $`A`$ are constant. The coefficients $`\gamma `$ and $`A`$ are related to the electron effective mass $`m^{}`$ as $`\gamma m^{}`$ and $`A(m^{})^2`$, respectively. The ratio $`A/\gamma ^2`$ therefore does not depend on $`m^{}`$. In fact, Kadowaki and Woods showed that many U- and Ce-based compounds show a universal relation, $`A/\gamma ^2`$ = 1.0$`\times `$10-5 $`\mu \mathrm{\Omega }`$cm (mol$``$K/mJ)2 . Furthermore, this relation has proved to be applicable to $`d`$-electron systems with large $`\gamma `$, for example, A15-type intermetallics like V3Si , nearly-ferromagnetic itinerant-electron systems like YCo2 , and metallic oxides close to metal-insulator transition like V2O3 under high pressure  and LiV2O4 . These observations demonstrate that the Fermi-liquid state is a general feature for a wide range of correlated-electron systems.

Large $`\gamma `$ has also been reported in a number of Yb-based intermetallics . One can naturally expects that the Kadowaki-Woods relation, $`A/\gamma ^2`$ = 1.0$`\times 10^5`$$`\mu \mathrm{\Omega }`$cm (mol$``$K/mJ)2, also holds for these Yb compounds. In several Yb-based compounds, however, the $`A/\gamma ^2`$ values have been reported to be remarkably smaller than that of the Kadowaki-Woods relation. For YbCu4Ag  and YbCu5-xAgx , the $`A/\gamma ^2`$ values are 0.1-0.6$`\times 10^6`$$`\mu \mathrm{\Omega }`$cm(mol$``$K/mJ)2, nearly two orders of magnitude smaller than that for the Kadowaki-Woods relation. It is also reported that the $`A/\gamma ^2`$ for YbCu4.5  and YbNi2Ge2  is close to this value. In addition, this value well coincides with the ratio for the transition metals such as Re, Os, Ni, and so on .

This deviation of $`A/\gamma ^2`$ value from the Kadowaki-Woods relation can pose quite an interesting subject to the Fermi-liquid theory, if it is a general phenomena for a class of materials. However, there have been no systematic studies on the $`A/\gamma ^2`$ values for Yb-based compounds. We have therefore investigated the $`A/\gamma ^2`$ relation in several Yb-based compounds. We have measured the electrical resistivity of the Yb-based compounds, YbAl2, YbInAu2, YbInCu4, and YbCuAl. These systems are typical examples of Yb-based intermediate-valent or heavy-fermion compounds. We also have examined the $`A/\gamma ^2`$ values for several other compounds using the values reported in literature.

## 2 Experimental

Polycrystalline samples of YbAl2 and YbCuAl have been prepared by argon arc melting and subsequent annealing. To compensate the loss of Yb due to evaporation, slightly additional amount of Yb was used in synthesis. Polycrystalline sample of YbInAu2 was prepared by melting the elements in a BN crucible placed in an evacuated silica tube, and slow cooling. For YbInCu4, a single crystal sample was prepared by an In-Cu flux technique . Powder x-ray diffraction shows that single phased samples were obtained for all the compounds. Electrical resistivity was measured by a standard dc four probe technique in the temperature range between 4.2 and 300 K.

## 3 Results

Figure 1 shows the electrical resistivity $`\rho `$ as a function of temperature $`T`$. The residual resistivity $`\rho _0`$ of these samples are almost the same as or smaller than those reported in the literature . $`\rho `$ of YbInCu4 decreases abruptly at 40 K due to the valence transition of Yb . The sharp transition indicates that our crystal is well ordered . YbCuAl shows relatively rapid decrease below approximately 20 K. This temperature roughly corresponds to the characteristic temperature $`T^{}`$, below which the coherence between Kondo singlets develops and the system enters the Fermi liquid regime . For YbInAu2, $`T^{}`$ is of the order of 70 K. For YbAl2, $`\rho `$ does not show a distinct temperature dependence up to 300 K. This indicates that $`T^{}`$ of YbAl2 is above the room temperature.

In Fig. 2, $`\rho \rho _0`$ are plotted as a function of $`T^2`$. For YbCuAl, YbInAu2, and YbAl2, $`\rho \rho _0`$ is described by the $`T^2`$ power law at low temperatures, indicating the evolution of Fermi-liquid state. For YbInCu4, $`\rho \rho _0`$ deviates from the $`T^2`$ dependence above 20 K, and the data up to 30 K are well fitted with the correction of $`T^5`$ dependence, as is shown in Fig. 2 (b). This suggests that the conventional electron-phonon scattering is important in YbInCu4.

The values of the $`T^2`$ coefficient $`A`$ have been obtained by fitting the data at low temperatures, and are listed in table 1. In these $`A`$ values, errors of the order of 20% can exist due to the inaccuracy in estimating the sample dimension. For YbAl2 and YbInCu4, however, the error in $`A`$ can be much larger because of the small value of $`A`$ and the presence of the $`T^5`$ term.

The $`A`$ values are plotted against $`\gamma `$ on the Kadowaki-Woods plot , as is shown in Fig. 3. We also plot $`A`$ and $`\gamma `$ values of several systems reported in literatures. The values of $`A`$ and $`\gamma `$ are listed in table 1.

In Fig. 3, one can see that the Kadowaki-Woods relation, $`A/\gamma ^2`$ = 1.0$`\times `$10-5 $`\mu \mathrm{\Omega }`$cm(mol$``$K/mJ)2, is almost preserved for YbNi2B2C, YbRh2Si2, Yb2Co3Ga9, CeNi, and YbInAu2. On the other hand, it is apparent that several systems show a significant deviation from the relation. In particular, there appears to exist another ’universal’ relation; $`A/\gamma ^20.4\times 10^6\mu \mathrm{\Omega }`$cm (mol$``$K/mJ)2, for YbCu5-xAgx, YbCu4.5, YbCuAl, YbNi2Ge2, YbAl3, YbInCu4, YbCu4Al, CeNi9Si4 and CeSn3. Extrapolation of this line well coincides with the $`A/\gamma ^2`$ value for the transition metals such as Pd or Re . As for YbAl2 and YbCu2Si2, the $`A/\gamma ^2`$ ratio appears to be situated between the two lines.

## 4 Discussion

We have shown in the preceding section that many Yb-based and several Ce-based compounds show nearly two times smaller values of $`A/\gamma ^2`$ than that for the Kadowaki-Woods relation. In this section, we discuss on the possible origin of the deviation from the Kadowaki-Woods relation.

At first, it must be remarked that the $`A`$ value depends not only on $`T_\mathrm{K}`$ but also on many factors, including anisotropy, carrier concentration, Fermi-surface topology, band structures, and site disorder. In particular, the effect of site disorder may be important as is pointed by several authors, since the effect can suppress $`A`$ through the Kondo-hole effect . Here, the site disorder gives the additional resistivity: $`\rho ^{\mathrm{disorder}}`$ = $`\rho _0BT^2`$ , which results in the reduced $`T^2`$ coefficient of $`AB`$. However, although this mechanism may be important in some systems, it is unlikely that the Kondo-hole effect can explain all the small $`A/\gamma ^2`$ values, especially almost universal value, $`A/\gamma ^2`$ = 0.4$`\times `$10-6 $`\mu \mathrm{\Omega }\mathrm{cm}(\mathrm{mol}\mathrm{K}/\mathrm{mJ})^2`$. Kondo-hole effect should result in a random distribution of the $`A/\gamma ^2`$ values. Moreover, the additional term, $`\rho ^{\mathrm{disorder}}`$ = $`\rho _0BT^2`$, has been observed in only limited systems, such as YbInAu2 under high pressures . Thus, we believe that the Kondo-hole effect is not the crucial origin for most of the small $`A/\gamma ^2`$ values. As for the other effect such as carrier concentration or band structures, although these effect must be taken into consideration, it is unlikely that these effect can explain the smaller ’universal’ relation.

We next consider this phenomenon relating with the three mechanisms; (i) single-body band effect, (ii) intersite magnetic correlation, and (iii) the ground state degeneracy.

### 4.1 Single-body band effect

Miyake et al. have considered theoretically the effect of many-body correlations in heavy-fermion systems, where conduction electrons have a strong frequency-dependence in its self energy. They have suggested that the many-body effect can enhance the $`A/\gamma ^2`$ value by about 25 times larger than the case of single-body band, and this would explain the 25 times different $`A/\gamma ^2`$ between the transition metals and the heavy-fermion systems .

Similar argument may be applicable for YbAl2, of which $`\gamma `$ is relatively small. In this compound, the many-body and the single-body effects can be comparable, which may reduce the $`A/\gamma ^2`$ to the same order as that in transition metals. On the other hand, for YbCuAl, YbCu4Ag, YbCu5 or CeNi9Si4, these systems exhibit much larger $`\gamma `$ (100-600 mJ/molK2) than those of transition metals. This indicates that DOS of the conduction band is enhanced through the many-body effect, i.e., the Kondo-lattice formation.

Even in YbAl3, for which the $`\gamma `$ value (45 mJ/mol$``$K2) may not be so large, the de-Haas van Alphen effect measurements have revealed that the Fermi surface of YbAl3 is strongly renormalized due to many-body effect of the localized 4$`f`$ moment and the conduction electrons . We therefore suppose that the single-body band effect is not dominating for these systems.

### 4.2 Intersite magnetic correlation

As is pointed in ref. , many U-based compounds on the Kadowaki-Woods line exhibit strong intersite magnetic-correlation, including magnetic ordering in UPt, UGa3 and UIn3, and distinct spin-fluctuations in UAl2 and UPt3. Magnetic correlation due to the Ruderman-Kittel-Kasuya-Yosida (RKKY) interaction is also considered to be important for those Ce- and Yb-based compounds such as CeAl3 , CeCu2Si2 , CeB6 , CeCu6, CeRu2Si2 , YbRh2Si2 , and so on. For $`d`$-electron systems such as LiV2O4 , YCo2  and (Y,Sc)Mn2 , the presence of strong magnetic correlation has been demonstrated by neutron scattering or NMR. It is notable that these compounds include both nearly-ferromagnetic (UAl2 , YCo2  etc.) and nearly-antiferromagnetic systems (CeCu6 , CeCu2Si2  etc.).

On the other hand, for the systems with the smaller $`A/\gamma ^2`$ value, magnetic correlation does not appear to be important. Physical properties are well explained using a single-impurity model in YbCu5 , YbCu5-xAgx , YbCu4Ag , YbCuAl , CeNi9Si4  and CeSn3 . Single-impurity character is also demonstrated by neutron scattering experiments for YbCuAl  and YbInCu4 . Therefore in these compounds, intersite magnetic correlation can be neglected. For YbCu4.5, magnetic ordering is not observed even at 235 kbar down to 50 mK , suggesting the weak RKKY interaction.

This remarkable contrast in the strength of magnetic interactions implies that there exist qualitatively different scattering mechanisms in the electrical resistivity. For the case with strong magnetic interactions, $`A`$ and $`\gamma `$ are enhanced both by the large density of state (DOS) at the Fermi energy ($`E_\mathrm{F}`$) and by the strong spin-fluctuations. In contrast, for the single impurity-like case, the large $`A`$ is solely attributed to the DOS at $`E_\mathrm{F}`$. One may hence consider that this difference is the possible origin of the two ’universal’ $`A/\gamma ^2`$ relations.

However, this tendency is inconsistent with the theoretical calculations based on the spin fluctuation theory . Takimoto et al. have shown that the value of $`A/\gamma ^2`$ is almost constant from the pure Kondo regime (single-impurity limit) to almost magnetically instability limit. The value of $`A/\gamma ^2`$ they estimated is close to the Kadowaki-Woods relation . Similar result is also reported by Continentino, who have shown that the $`A/\gamma ^2`$ value is independent of the distance from magnetic instability .

It should also be noted that there exist some exceptions of the above tendency. In CePd3, intersite magnetic correlation is considered to be of minor importance . For YbInAu2 or Nb3Sn, no evidence of strong magnetic-correlation is reported. However, $`A/\gamma ^2`$ values in these systems are close to the Kadowaki-Woods relation. On the other hand, Pd and Pt show the small $`A/\gamma ^2`$ value, though they are well-known examples of nearly-ferromagnetic metals . Therefore, these findings may not justify the above scenario, in which strong intersite magnetic-correlation enhances $`A/\gamma ^2`$ values.

### 4.3 Ground state degeneracy

One may notice that most of the systems with the smaller $`A/\gamma ^2`$ values in Fig. 3 are classified as the intermediate-valent compounds, where crystal-field splitting, $`\mathrm{\Delta }_{\mathrm{CF}}`$, is of minor importance, and the full degeneracy $`N`$ for Yb3+ or Ce3+ ion is almost preserved . In fact, physical properties of YbCu4Ag, YbCuAl, CeSn3 and CeNi9Si4 are explained by the impurity model for $`N`$ = 8 (Yb3+) or $`N`$ = 6 (Ce3+), as is noted in the preceding subsection. For YbAl3 and YbAl2, Shimizu et al. have suggested by the 171Yb-NMR that the $`N`$ = 8 ground state is well conserved in these compounds . Even in YbCu5, which exhibits a large $`\gamma =550`$ mJ/mol$``$K2, $`\mathrm{\Delta }_{\mathrm{CF}}`$ is considered to be comparable with the Kondo temperature $`T_\mathrm{K}`$, and the low temperature properties are characterized by $`N`$ = 4

On the contrary, the systems such as CeCu6, CeAl3 and CeCu2Si2 are considered to be affected by the crystal-field effect, which reduce the ground state degeneracy down to $`N`$ = 2 .

The difference in $`N`$ is related to the magnitude of the magnetic moment which participate in the Fermi-liquid formation. It can therefore affect on the $`A/\gamma ^2`$ values. We note that the difference between $`N`$ 4 and $`N`$ 3 states can be crucial. Theoretical calculation predicts that the DOS has a peak situated above $`E_\mathrm{F}`$ for the case of $`N`$ 4, whereas the peak is positioned just at $`E_\mathrm{F}`$ for $`N`$. Similarly, magnetic excitation spectra also show inelastic structure for large $`N`$ . Hence, we suppose that in those Yb- and Ce-based intermediate-valent systems, their largely-degenerated states ($`N4`$) develop the excitation spectra with qualitatively different shape from that in those heavy-fermion systems with small $`N`$ ($``$ 3), resulting in the significant difference in the $`A/\gamma ^2`$ values. There have been no theories for the $`N`$ dependence of $`A/\gamma ^2`$ value as far as we know. Theoretical investigation for the relation between $`N`$ and $`A/\gamma ^2`$ is desired .

However, some exceptions for this understanding should be noted. For Yb2Co3Ga9 , the full degeneracy for Yb3+ is considered to be preserved, though they exhibit the same order of $`A/\gamma ^2`$ as that for the Kadowaki-Woods relation. In addition, it is unclear whether all the U-based compounds on the Kadowaki-Woods line can be understood in terms of $`N3`$ ground states. In these U-compounds, the enhanced low-energy excitations due to intersite magnetic correlation may also be responsible.

We also note that CePd3 is again exceptional. This compound is a typical intermediate-valent compound. The full degeneracy $`N`$ = 6 is considered to be preserved, and the intersite magnetic correlation is also of minor importance . Nevertheless, this compound show the same order of $`A/\gamma ^2`$ value as that of heavy-fermion compounds. However, it should be remarked that the carrier concentration of CePd3 is unusually small ($``$ 0.3 per unit cell) , and hence this compound would be close to Kondo-insulators. This situation cannot allow us to make a naive comparison for CePd3.
Finally, an important suggestion is given experimentally from the electrical resistivity measurement under pressures. Knebel et al.  have examined the $`AT_{\mathrm{max}}^2`$ of YbNi2Ge2 under pressure, where $`T_{\mathrm{max}}`$ is the maximum temperature of the resistivity adhering to a $`T^2`$ power-law, and should be proportional to $`\gamma ^1`$. The value of $`AT_{\mathrm{max}}^2`$ is therefore a measure of $`A/\gamma ^2`$. They have found that $`AT_{\mathrm{max}}^2`$ increases by a factor about 25 times under high pressures. Similar variation of $`AT_{\mathrm{max}}^2`$ under pressure has also been reported for CeCu2Si2 . These phenomena are most likely related to either of the change of the intersite magnetic correlation or that of the ground state degeneracy. Hence, performing similar experiments on much more systems may eventually reveal the underlying origin of the two ’universal’ $`A/\gamma ^2`$ relations.

In addition, the effect of disorder must be carefully taken into consideration. If the disorder makes little effect on the host-material properties, its effect on the resistivity would be described by the Kondo-hole effect, which reduces $`A`$. On the contrary, in most of systems, disorder is considered to affect the whole range of electrical properties in the Kondo-lattice formation. It would reduce the characteristic temperature $`T^{}`$, which results in the enhanced $`A`$ values. This may be the case in YbInAu2, where site disorder easily occur because of its crystal structure. Therefore, the $`A/\gamma ^2`$ values in several systems may not be intrinsic. Experimental works using high quality samples are particularly important.

## 5 Summary

We have measured the electrical resistivity and have examined the $`A/\gamma ^2`$ values of YbAl2, YbInAu2, YbInCu4 and YbCuAl. We have also plotted $`A`$ vs. $`\gamma `$ for several systems reported in literature. The result reveals that the $`A/\gamma ^2`$ values are not unique among materials, but varies in the range of 0.4$`\times `$10-6 \- 1.0$`\times `$10-5 $`\mu \mathrm{\Omega }`$cm(mol$``$K/mJ)2. In particular, it has been found that there exists another ’universal’ relation; $`A/\gamma ^2`$ = 0.4$`\times `$10-6 $`\mu \mathrm{\Omega }`$cm(mol$``$K/mJ)2, for a number of systems including YbCuAl, YbAl3, YbInCu4, YbCu4Al as well as YbCu5, YbCu4.5, YbCu4Ag, YbNi2Ge2, CeNi9Si4 and CeSn3. This value of $`A/\gamma ^2`$ is about 25 times smaller than that known in the Kadowaki-Woods relation; $`A/\gamma ^2`$ = 1.0$`\times `$10-5 $`\mu \mathrm{\Omega }`$cm(mol$``$K/mJ)2.

To explain this deviation, several possible mechanisms have been discussed. The Kondo-hole effect or the single-body-band effect may be applicable for some systems. However, these two mechanisms cannot explain the almost ’universal’ nature of the smaller $`A/\gamma ^2`$ values. Thus, we have considered the tendency of these compounds empirically, and have focused on the intersite magnetic correlation and the ground state degeneracy.

As for the former, we have pointed that most of the systems with the smaller $`A/\gamma ^2`$ value exhibit single-impurity like behavior. This suggests that the intersite magnetic interactions are negligible in these systems. In contrast, many systems on the Kadowaki-Woods line are known to show strong magnetic correlation. This tendency is valid for many compounds plotted in Fig. 3. However, this interpretation is inconsistent with the theoretical results based on the spin-fluctuation theory.

As for the latter, it has been found that the ground state degeneracy $`N`$ differs largely between the systems with the smaller $`A/\gamma ^2`$ and those on the Kadowaki-Woods line. Almost all the systems with the smaller $`A/\gamma ^2`$ values (except for $`d`$-electron systems) show largely degenerated ground state; i.e., $`N`$ 4. On the other hand, those on the Kadowaki-Woods line are considered to have $`N3`$ state due to the crystal-field splitting. Since this difference can affect on the magnitude of the magnetic moment as well as the shape of the excitation spectra, the $`A/\gamma ^2`$ values may also vary depending on $`N`$.

For both the cases, i.e., the intersite magnetic correlation and the ground state degeneracy, our interpretations are only empirical. Hence, theoretical confirmations are strongly desired.

## Acknowledgments

Authors gratefully acknowledge T Takimoto, S Kambe, K Miyake, J M Lawrence, G Hilscher, H Kitazawa and H Suzuki for valuable discussion and suggestions.

## References