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# Mechanical relaxation in glasses and at the glass transition

## I Introduction

Relaxation in glasses, sometimes also called secondary relaxation to distinguish it from the primary relaxation at the glass transition, is generally believed  to be well described in terms of the Arrhenius-Kramers picture , with a relaxation time $`\tau _V`$ given by the Arrhenius relation

$$\tau _V=\tau _0\mathrm{e}^{V/k_BT},$$
(1)
where $`\tau _0`$ is a microscopic time of the order of 10<sup>-13</sup> seconds, $`V`$ is the energy of the barrier between two energy minima of the system, and $`T`$ is the temperature.

In contrast, the primary relaxation or $`\alpha `$-process, the onset of the flow process at the glass transition temperature $`T_g`$ and above, seems to follow a much steeper law

$$\tau _\alpha =\tau _0\mathrm{e}^{A/(TT_0)},$$
(2)
where $`A`$ and $`T_0`$ are constants with the dimension of a temperature. This is the well-known empirical Vogel-Fulcher-Tamman (VFT) or Williams-Landel-Ferry (WLF) equation. $`T_0`$, the Vogel-Fulcher temperature, is smaller than $`T_g`$; the closer it lies to $`T_g`$, the more fragile is the glass former.

Since the Arrhenius law has a sound microscopic background  and the VFT or WLF equation has not, it seems reasonable to build a joint quantitative description on the former, bearing in mind the physical difference of the two processes. This is the intention of the present paper.

In glasses, one has to reckon with a whole distribution of relaxational jumps, not only over different potential barrier heights, but also between energy minima of different energy. Thus one has to extend the classical Arrhenius-Kramers treatment  of a thermally activated relaxation process in a symmetric double-well potential to deal with a broad distribution of barrier heights and asymmetries. A distribution in the barrier heights was first considered by Fröhlich , but only for symmetric potentials. An asymmetric multiminimum situation was solved by Hoffman and Pfeiffer . But none of these early attempts dealt simultaneously with a broad distribution in both quantities, the barrier height and the asymmetry of the wells. The necessity of such a double distribution was first recognized in the tunneling model for the two-level states below 1 K  in 1971. Ten years later, Gilroy and Phillips  extended the scheme to classical relaxation processes. Also, they were the first to draw a parallel between mechanical relaxation data and the quasielastic part of the Raman scattering. At the end of the same decade, the soft potential model postulated a relation between the tunneling states and the low barrier classical relaxation processes in glasses . Nevertheless, up to now only few checks of these postulates for dynamical mechanical , Raman  and neutron  data have been reported in the literature.

The present paper begins in Section II with a discussion of the Gilroy-Phillips model, and a derivation of its connection to rheology. It turns out that one can define a barrier distribution function $`f(V)`$ to describe the mechanical shear relaxation at different temperatures and frequencies. The integral of this barrier distribution function over all barrier heights $`V`$ must equal 1 to bring the shear modulus down to zero. In order to include the flow process into the same scheme, one separates $`f(V)`$ into two parts, $`f_s(V)`$ and $`f_\alpha (V)`$. The first of these describes the secondary relaxations in the glass phase, the second describes the $`\alpha `$-process in the undercooled liquid, respectively. As will be seen, the sum rule for the total barrier distribution function supplies a quantitative basis for Angell’s conjecture  of a relation between the fragility and the rise of the fast picosecond process above the glass transition. The low-barrier part of $`f_s(V)`$ determines the relaxational part of neutron and Raman scattering. The corresponding equations are derived.

Section III applies the equations to determine $`f(V)`$ from literature data for amorphous polystyrene, vitreous silica and a sodium silicate glass. From the results, one gets a first impression as to whether one gets the same secondary barrier distribution function from different methods, in particular if one compares the high frequency neutron, Raman and Brillouin scattering results with the low frequency torsion pendulum or creep data. Furthermore, one gets a feeling for the amount of reduction of the shear modulus by the secondary relaxation processes in the glass phase. As we will see, the findings suggest a generalized Maxwell criterion for the onset of the glass transition, namely that the flow begins when the shear response from the secondary relaxation equals the elastic one. Section IV compiles and discusses these results and their possible significance for our view of the glass transition. Summary and conclusions are given in Section V.

## II The Gilroy-Phillips model

### A The asymmetric double-well potential

Let us denote the shear strain by $`ϵ`$, the shear stress by $`\sigma `$ and the (infinite frequency) shear modulus by $`G`$. $`G`$ will generally depend on the temperature $`T`$.

The structural relaxation is taken to be a superposition of independent Debye relaxation centers in asymmetric double-well potentials with two minima, as shown in Fig. 1. The energy of the left minimum is $`\mathrm{\Delta }/2`$ and the energy of the right minimum is $`+\mathrm{\Delta }/2`$. The height of the barrier is $`V`$.

The interaction between the shear strain and the Debye relaxation center is described by the change of the asymmetry $`\mathrm{\Delta }`$ under the influence of the strain. The interaction is characterized by the coupling parameter $`\gamma `$, leading to an asymmetry $`\mathrm{\Delta }+\gamma ϵ`$ of the relaxation in the strained glass. $`\gamma `$ must be considered to depend both on $`V`$ and $`\mathrm{\Delta }`$.

The free energy $`F`$ of the relaxation center reads

$$F=k_BT\mathrm{ln}\left[2\mathrm{cosh}\left(\frac{\mathrm{\Delta }+\gamma ϵ}{2k_BT}\right)\right],$$
(3)
which has the second derivative with respect to the shear distortion $`ϵ`$

$$\frac{^2F}{ϵ^2}=\frac{\gamma ^2}{4k_BT\mathrm{cosh}^2(\mathrm{\Delta }/2k_BT)}$$
(4)
The second derivative determines the contribution of that specific relaxing entity to the difference between the shear moduli at infinite and zero frequency. The equation shows that the main influence on the shear modulus is due to relaxation in potentials with asymmetries smaller than $`k_BT`$; for larger asymmetries the influence decreases rapidly because of the square of the hyperbolic cosine in the denominator.

### B The barrier distribution function $`f(V)`$

We want to calculate the frequency dependence of the shear modulus under the assumption of slowly varying distribution functions in the parameters $`V`$ and $`\mathrm{\Delta }`$. In detail, we assume a number density of relaxing entities $`n(V,\mathrm{\Delta })`$ and a coupling constant $`\gamma (V,\mathrm{\Delta })`$ which are both approximately constant if either $`V`$ or $`\mathrm{\Delta }`$ is varied by an amount of the order of the thermal energy $`k_BT`$.

Under this assumption, it is safe to neglect as well the influence of the asymmetry on the relaxation time. We assume the relaxation time $`\tau _V`$ to be given by the Arrhenius equation (1).

We then integrate over the asymmetry $`\mathrm{\Delta }`$ to obtain the step $`\delta G`$ between the shear moduli at infinite and zero frequency from all relaxation centers with barrier height between $`V`$ and $`V+dV`$

$$\delta G=dV_{\mathrm{}}^{\mathrm{}}\frac{\gamma ^2n(V,\mathrm{\Delta })d\mathrm{\Delta }}{4k_BT\mathrm{cosh}^2(\mathrm{\Delta }/2k_BT)}$$
(5)
Since one has only contributions in the near neighborhood of $`\mathrm{\Delta }=0`$, where $`n(V,\mathrm{\Delta })n(V,0)`$, and since

$$_{\mathrm{}}^{\mathrm{}}\frac{d\mathrm{\Delta }}{\mathrm{cosh}^2(\mathrm{\Delta }/2k_BT)}=4k_BT,$$
(6)
one finds

$$\delta G=\gamma ^2n(V,0)dV.$$
(7)
This is different from a single relaxation in a symmetric potential, where the step in the modulus is inversely proportional to the temperature. The physical reason for this difference is clear: As the temperature rises, relaxation centers with higher and higher asymmetry begin to contribute to the step in the modulus. This is an important difference between relaxation in crystals and relaxation in disordered matter.

The temperature-independent step in the modulus is determined by the barrier distribution function $`f(V)`$, defined by

$$f(V)=\frac{\gamma ^2n(V,0)}{G}.$$
(8)
This parameter combination can be argued to remain independent of temperature, even if $`G`$ varies with temperature, considering the relaxing entity as a small misfit region in an elastic medium , a misfit region which is able to change the sign of the misfit by jumping over the barrier. Here, however, this argument will not be given in detail.

The frequency dependence of the complex shear modulus at the frequency $`\omega `$ and the temperature $`T`$ reads

$$\frac{G^{}(\omega ,T)}{G}=\frac{G_e}{G}+_0^{\mathrm{}}f(V)\frac{dV}{1+\omega ^2\tau _V^2}$$
(9)
$$\frac{G\mathrm{"}(\omega ,T)}{G}=_0^{\mathrm{}}f(V)\frac{\omega \tau _VdV}{1+\omega ^2\tau _V^2},$$
(10)
where $`\tau _V`$ is a function of $`V`$ by the Arrhenius relation eq. (1), and $`G_e`$ is the zero frequency modulus after the decay of all the relaxations in the system.

These two equations describe the real and the imaginary part of the frequency-dependent shear modulus at all frequencies and temperatures. As long as one can reckon with a temperature-independent number of uncoupled relaxation centers, the barrier distribution function $`f(V)`$ remains temperature-independent.

But even if $`f(V)`$ depends on temperature, it can still be formally used to characterize the shear relaxation. As shown in the next subsection, one can rewrite the conventional rheological expressions  in terms of $`f(V)`$. The advantage of the choice of $`f(V)`$ lies in the possibility to distinguish the trivial Arrhenius temperature dependence from other, nontrivial temperature changes. These nontrivial temperature changes will then reflect in a temperature dependence of $`f(V)`$.

### C Rheological equations in terms of $`f(V)`$

Comparing the two expressions, equs. (9) and (10), to those in the textbooks, for instance the one on polymers by Ferry  (chapter 3, equs. (23) and (24)), one finds the relation between the rheological relaxation function $`H(\tau )`$ and the barrier distribution function $`f(V)`$

$$H(\tau _0\mathrm{e}^{V/k_BT})=H(\tau _V)=Gk_BTf(V).$$
(11)
With this equation, one can rewrite all the exact and approximate rheological relations  in terms of $`f(V)`$. To do this, one first has to define a convenient equivalent function $`l(V)`$ to the conventional rheological function $`L(\tau )`$, which is needed whenever one wants to calculate a compliance

$$L(\tau _0\mathrm{e}^{V/k_BT})=L(\tau _V)=\frac{k_BTl(V)}{G}.$$
(12)
In the following, the most important equations of chapter 3 of Ferry’s book  are translated into the Gilroy-Phillips notation. Ferry’s equation (19) for the time-dependent modulus $`G(t)`$ reads

$$G(t)=G_e+_{\mathrm{}}^{\mathrm{}}H(\tau )\mathrm{e}^{t/\tau }d\mathrm{ln}\tau $$
(13)
and translates into

$$G(t)=G_e+G_0^{\mathrm{}}f(V)\mathrm{e}^{t/\tau _V}𝑑V.$$
(14)
For a viscoelastic liquid, the zero frequency modulus $`G_e=0`$, so one must have

$$_0^{\mathrm{}}f(V)𝑑V=1.$$
(15)
This is the sum rule for the barrier distribution function $`f(V)`$. It has important consequences for the connection between primary and secondary relaxation, as discussed in the next subsection.

Next, there is Ferry’s eq. (20) for the compliance

$$J(t)=\frac{1}{G}+_{\mathrm{}}^{\mathrm{}}L(\tau )(1\mathrm{e}^{t/\tau })d\mathrm{ln}\tau +\frac{t}{\eta _0},$$
(16)
where $`\eta _0`$ is the viscosity, which translates into

$$J(t)=\frac{1}{G}\left[1+_0^{\mathrm{}}l(V)(1\mathrm{e}^{t/\tau _V})𝑑V\right]+\frac{t}{\eta _0}.$$
(17)
The viscosity $`\eta _0`$ can be calculated from Ferry’s eq. (28)

$$\eta _0=_{\mathrm{}}^{\mathrm{}}\tau H(\tau )d\mathrm{ln}\tau ,$$
(18)
which translates into

$$\eta _0=G_0^{\mathrm{}}\tau _Vf(V)𝑑V.$$
(19)
Ferry’s equs. (21) and (22), the transformation from $`H(\tau )`$ to $`L(\tau )`$ and back, read

$$L=\frac{H}{\left[G_e_{\mathrm{}}^{\mathrm{}}\frac{H(u)}{\tau /u1}d\mathrm{ln}u\right]^2+\pi ^2H^2}$$
(20)
and

$$H=\frac{L}{\left[\frac{1}{G}+_{\mathrm{}}^{\mathrm{}}\frac{L(u)}{1u/\tau }d\mathrm{ln}u\frac{\tau }{\eta _0}\right]^2+\pi ^2L^2}.$$
(21)
They translate into

$$l(V)=\frac{f(V)}{\left[\frac{G_e}{G}I_f(V)\right]^2+(\pi k_BTf(V))^2}$$
(22)
with

$$I_f(V)=_0^{\mathrm{}}\frac{f(E)dE}{\mathrm{exp}((VE)/k_BT)1}$$
(23)
and

$$f(V)=\frac{l(V)}{\left[1\frac{\tau _VG}{\eta _0}+I_l(V)\right]^2+(\pi k_BTl(V))^2}$$
(24)
with

$$I_l(V)=_0^{\mathrm{}}\frac{l(E)dE}{1\mathrm{exp}((EV)/k_BT)}.$$
(25)
With these exact equations, one can calculate the mechanical response for any type of shear experiment for a given barrier distribution function $`f(V)`$. The reverse, the determination of $`f(V)`$ from experimental data, is more difficult, because the exact equations are integral equations. Nevertheless, one can start to determine a first approximation to $`f(V)`$ from measurements of $`G^{}`$ and $`G\mathrm{"}`$ using the crude approximations

$$\frac{G^{}}{G}=1_0^{k_BT\mathrm{ln}(1/\omega \tau _0)}f(V)𝑑V$$
(26)
and

$$f(k_BT\mathrm{ln}(1/\omega \tau _0))=\frac{2}{\pi }\frac{G\mathrm{"}}{Gk_BT}.$$
(27)
### D Primary and secondary relaxation

It is quite clear that one needs to distinguish secondary and primary processes, because their physical mechanism is different. Thus one has to distinguish between $`f_s(V)`$, the secondary barrier distribution function of the secondary Arrhenius relaxation, and $`f_\alpha (V)`$, the primary barrier distribution function for the primary $`\alpha `$-process or flow process (see Fig. 2).

As is well established , $`H_\alpha (\tau /\tau _\alpha )`$ is independent of the temperature. This is the time-temperature scaling of the $`\alpha `$-process, sometimes also denoted as thermorheological simplicity. Since the factor $`Gk_BT`$ in eq. (11) between $`H(\tau )`$ and $`f(V)`$ varies only weakly with temperature, this implies that the primary barrier distribution function $`f_\alpha (V)`$ is an essentially temperature-independent function of $`VV_\alpha (T)`$, where $`V_\alpha (T)`$ denotes the maximum of this strongly peaked function. From the Vogel-Fulcher law eq. (2), one expects the temperature dependence

$$V_\alpha (T)=V_\alpha (T_g)\frac{T(T_gT_0)}{T_g(TT_0)},$$
(28)
showing the divergence of the fictive Arrhenius barrier of the flow process towards the Vogel-Fulcher temperature $`T_0`$.

If time-temperature scaling holds, the weight $`w_\alpha `$ of the $`\alpha `$-process, given by

$$w_\alpha =_0^{\mathrm{}}f_\alpha (V)𝑑V$$
(29)
should be temperature-independent. In the comparison to experiment, we will see that $`w_\alpha `$ tends to be close to 1/2.

What does this imply for the secondary relaxations? The $`\alpha `$-process is also an upper cutoff for the secondary relaxation; at the end of the process, the long time shear modulus is zero. If a secondary relaxation barrier is too high, the relaxing entity will flow away before it has a chance to jump. Therefore there is a steep cutoff for the secondary barrier distribution function $`f_s(V)`$ at $`V_\alpha (T)`$. According to the sum rule eq. (15)

$$_0^{V_\alpha (T)}f_s(V)𝑑V=1w_\alpha =\mathrm{const}\frac{1}{2}.$$
(30)
With this sum rule, the decrease of $`V_\alpha (T)`$ with increasing temperature implies that the secondary barrier distribution function $`f_s(V)`$ must increase with increasing temperature. This increase will be stronger for more fragile glass formers. Such a connection between the fragility and the rise of the fast process above $`T_g`$ has been indeed postulated empirically ; here we will be able to quantify this connection.

The increase of $`f_s(V)`$ above the glass temperature can be characterized to first order by

$$f_s(V)=f_s(V,T_g)\left[1+\alpha _s(V)\frac{TT_g}{T_g}\right].$$
(31)
One can define an average temperature coefficient $`\overline{\alpha _s}`$ by

$$\overline{\alpha _s}=\frac{1}{1w_\alpha }_0^{V_\alpha (T_g)}\alpha _s(V)f_s(V)𝑑V.$$
(32)
Differentiating the sum rule eq. (30) for $`f_s(V)`$ with respect to the temperature, calculating the derivative of $`V_\alpha (T)`$ with respect to temperature from eq. (28) and using eq. (32), one finds the relation between the fragility and the average rise of the secondary relaxation

$$\frac{T_0}{T_gT_0}=\frac{\overline{\alpha _s}(1w_\alpha )}{V_\alpha (T_g)f_s(V_\alpha (T_g))}.$$
(33)
This relation will become clearer in the next subsection, where the simplest possible case of a constant secondary barrier distribution function is discussed.

### E The generic case $`f_s(V)=`$ const

The deep implications of the Gilroy-Phillips formulation of the $`\alpha `$-process are more clearly seen in the simplest possible case, shown in Fig. 2. Let us assume $`f_s(V)=\mathrm{const}`$ and $`\alpha _s(V)=\mathrm{const}`$. If the rise of $`f_s(V)`$ with temperature is strictly linear, equs. (30) and (31) imply

$$V_\alpha (T)=\frac{V_\alpha (T_g)T_g}{T_g+\alpha _s(TT_g)},$$
(34)
which is not exactly equal, but very close to the empirical Vogel-Fulcher-Tamman or Williams-Landel-Ferry equation (2), with the Vogel-Fulcher temperature $`T_0`$ given by

$$T_0=T_g\left(1\frac{1}{\alpha _s}\right).$$
(35)
It is obvious how this comes about: at $`T_0`$, the density of secondary processes extrapolates to zero. Thus one has to proceed to infinitely high barriers to satisfy the sum rule (30). This gives a completely new view on the puzzling fragility of glass formers: the abnormal temperature dependence is a consequence of the time-temperature scaling of the $`\alpha `$-process, and of a strictly linear rise of the number of secondary relaxing units with temperature.

The decrease of the secondary barrier distribution function $`f_s(V)`$ implies a decrease of the number of minima of the glass former. Thus one gets an equality  between the Vogel-Fulcher and the Kauzmann temperature $`T_K`$, the latter being defined as the temperature where the excess entropy of the glass former over the corresponding crystalline system extrapolates to zero. If there are no minima between which the glass former can jump, there is no excess entropy, the old Adam-Gibbs idea .

Note that eq. (35) for the Vogel-Fulcher or Kauzmann temperature holds not only in the generic case of a constant secondary barrier distribution function, but for any $`f_s(V)`$, as long as one can reckon with the same strictly linear temperature rise of the function for all $`V`$.

To complete the discussion of the glass transition peculiarities  in the Gilroy-Phillips picture, let us look at the stretching of the $`\alpha `$-process, empirically described by the Kohlrausch equation

$$G(t)=G_\alpha \mathrm{exp}\left((\tau /\tau _\alpha )^\beta \right),$$
(36)
where the Kohlrausch exponent $`\beta `$ lies  between 0.3 and 0.7, and $`G_\alpha `$ is a free parameter. The smaller $`\beta `$ is, the more stretched is the $`\alpha `$-relaxation, and the stronger it deviates from a simple exponential decay.

In order to calculate $`\beta `$, the definition of the primary barrier distribution function $`f_\alpha (V)`$ must be more specific. Let us assume a gaussian centered at $`V_\alpha `$ with weight $`w_\alpha =1/2`$ and with a full width at half maximum (FWHM) denoted by $`\mathrm{\Delta }_\alpha `$. Calculating $`G(t)`$ from eq. (13), one then finds fairly Kohlrausch-like curves for the simple generic case of Fig. 2, at least in the time region of the $`\alpha `$-process, with $`G_\alpha \mathrm{0.55..0.75}G`$ and $`\tau _\alpha `$ about 80 % of the Arrhenius value for $`V_\alpha `$. There is a deviation of the Kohlrausch fits from the calculated curves, but it is so small that it would be hard to see in an experiment. It turns out that the ratio $`\mathrm{\Delta }_\alpha /V_\alpha `$ determines the Kohlrausch exponent $`\beta `$; if it is 0.05, then $`\beta 0.7`$; for the ratio 0.1, $`\beta 0.5`$ and for the ratio 0.2, $`\beta 0.3`$. So the broader $`f_\alpha (V)`$, the more stretched the relaxation, not unexpected.

Note this is merely a change of description. The Gilroy-Phillips formulation does not really explain the puzzling features of the glass transition, the fragility, the entropy crisis and the stretching. But it supplies a description which allows to look for a new kind of explanation. We will return to this point in the discussion.

In order to measure $`\alpha _s(V)`$ in the picosecond range by scattering methods, one still needs the equations for the neutron and Raman scattering functions in terms of the barrier distribution function. These will be derived in the next subsection, the last part of the description of the Gilroy-Phillips model.

### F Neutron and Raman scattering

One can carry out the same integrations over asymmetries and barrier heights as in the shear relaxation for the neutron scattering cross section. Let us begin with a single asymmetric double well, let us assume that atom $`j`$ has a coherent scattering length $`b_j`$ and an incoherent scattering cross section $`\sigma _j`$, and that it jumps from the position $`\stackrel{}{d}_j/2`$ to $`\stackrel{}{d}_j/2`$, with the origin of the coordinate system in the middle between the two.

For the incoherent inelastic scattering in the one-phonon approximation , it suffices to calculate the mean square displacements. These can be obtained from the Boltzmann occupation factors of the two minima of the potential. The average position vector $`\stackrel{}{r}_j`$ of atom $`j`$ is given by

$$<\stackrel{}{r}_j>=\frac{\stackrel{}{d}_j}{2}\mathrm{tanh}\frac{\mathrm{\Delta }}{2k_BT}$$
(37)
and its average square is

$$<\stackrel{}{r}_j^{2}>=\frac{d_j^2}{4},$$
(38)
so the mean square displacement contribution of the relaxation to atom $`j`$ reads

$$<u_j^2>=<\stackrel{}{r}_j^{2}><\stackrel{}{r}_j>^2=\frac{d_j^2}{4\mathrm{cosh}^2\mathrm{\Delta }/2k_BT}.$$
(39)
In this expression, we recognize the same inverse $`\mathrm{cosh}^2`$ as in eq. (4), which can be again integrated over the asymmetries, if the jump eigenvector stays essentially the same for the different local asymmetries.

The scattering contribution is a Lorentzian with a half width at half maximum in $`\omega `$ given by the inverse relaxation time, determined by the barrier height according to the Arrhenius equation (1). The weight of the contribution in $`S(Q,\omega )`$ is determined by the number of relaxations and the weighted sum of the jump vectors

$$d^2=\frac{_j\sigma _jd_j^2}{\overline{\sigma }}.$$
(40)
The sum is over all atoms in the sample, and $`\overline{\sigma }`$ is their average incoherent cross section.

Integrating over the barrier heights as well, one gets the equation for the incoherent scattering

$$S_{inc}(Q,\omega )=v_an(k_BT\mathrm{ln}\frac{1}{\omega \tau _0},0)\frac{k_B^2T^2Q^2d^2}{3\omega },$$
(41)
where $`v_a`$ is the atomic volume, and the prefactor $`1/3`$ stems from the directional average. This equation is again an approximation, which holds if $`f(V)`$ does not vary strongly with $`V`$. The coherent scattering is obtained replacing $`d^2`$ by $`d_{coh}^2(Q)`$ with

$$d_{coh}^2(Q)=\frac{3}{\overline{b}^2Q^2}<\underset{j}{}b_j\mathrm{e}^{i\stackrel{}{Q}\stackrel{}{R}_j}\stackrel{}{Q}\stackrel{}{d}_j^2>,$$
(42)
where $`\stackrel{}{R}_j`$ is the equilibrium position of atom $`j`$, $`\overline{b}`$ is the average scattering length and the brackets indicate the orientational averaging over the structure factor of the relaxation. Even after this averaging, the structure factor need not show a simple $`Q^2`$ behaviour like the incoherent one, but does still contain information on the jump vectors .

The scattering measurements do not give $`f(V)`$, but rather the product $`n(V,0)d^2`$. If one wants the proportionality factor between those two quantities, one needs additional information about the relaxing entities. However, there is an elegant and general way to obtain this proportionality factor for very low barriers from the soft potential model , which describes the tunneling states and the low-barrier classical relaxation as similar modes with a double-well potential distribution. It is not very difficult to derive an equation for the barrier distribution function $`f(V)`$ as defined here in terms of the definitions in this paper. One finds

$$f_{sp}(V)=\frac{2C}{W^{3/4}V^{1/4}},$$
(43)
where $`C`$ (in principle $`C_l`$ for longitudinal waves and $`C_t`$ for transverse waves) is a dimensionless constant of the order of $`10^4`$, which can be taken from acoustic attenuation measurements below 4 K, and $`W`$ is the crossover energy between tunneling and vibrational modes, which can be measured from the crossover regions of the specific heat or the thermal conductivity at low temperatures . The soft potential model has a fourth parameter $`P_s`$ for the density of these modes. With this parameter, the relation between $`n(V,0)d^2`$ and the secondary barrier distribution function $`f_s(V)`$ reads

$$v_an(V,0)d^2\frac{2W^2\rho C_t}{\mathrm{}^2P_s}=f_s(V),$$
(44)
where $`\rho `$ is the mass density. For glasses consisting of more than one sort of atoms, the relation might fail if strongly and weakly scattering atoms have different jump widths. But with this relation, one can determine the secondary barrier distribution function $`f_s(V)`$ from neutron scattering measurements without adaptable parameter, using soft potential parameters from the literature .

The Raman scattering from relaxations in glasses is not so easily calculated. However, experience  shows that neutron and Raman scattering give the same spectra as long as one stays at frequencies well below the boson peak. Thus one can use the Raman spectra as one uses incoherent neutron scattering data, with the disadvantage of an additional general adaptable parameter for the overall intensity. The advantage of the Raman technique is a much higher intensity and a much better resolution, allowing one to assess much lower frequencies.

## III Comparison to experiment

### A Values from different techniques

Let us first consider which barriers one samples with a given technique. Creep measurements cover the time range from 0.1 seconds to several weeks. This is a measurement in the time domain, applied mostly to measurements of the $`\alpha `$-process at the glass transition, where one should not use the Arrhenius relation eq. (1). Nevertheless, one can formally calculate barrier heights of the order of 27 to 41 $`k_BT_g`$, around 1 eV for polystyrene ($`T_g=373K`$) and around 4 eV for vitreous silica ($`T_g=1473K`$).

The torsion pendulum method with frequencies around 1 Hz sees relaxations around 0.1 seconds. In terms of the Arrhenius relation with $`\tau _0=10^{13}s`$, this implies a barrier height of 50 meV at 20 K. In order to get to 1 eV, one has to rise the temperature by a factor of twenty, thus getting close to the glass temperature of polystyrene.

Proceeding to higher frequencies, on has the vibrating reed measurements around 10 kHz, ultrasonic data in the MHz range, light scattering Brillouin data around 10 GHz and, finally, Raman and neutron data between a few GHz and a few hundred GHz. For the latter two, the lower limit holds only for the Raman technique; if one looks for the weak quasielastic scattering from secondary relaxations, the neutron technique in practice has a lower limit of 100 GHz. The upper limit of about 300 GHz is given by the crossover from relaxational to vibrational scattering . Thus one sees only the uppermost frequency band of the relaxational scattering with neutrons. Nevertheless, neutrons play an important role, because they serve to validate the Raman scattering data.

For the fast relaxation at 200 GHz, the relaxation time is of the order of a picosecond, only ten times longer than the microscopic time scale of the vibrational motion. The Arrhenius relation translates this again into a barrier of 50 meV at 300 K. Thus neutron and Raman measurements at room temperature sample the same relaxations that one sees in a torsion pendulum measurement around 20 K. If one is still in the glass phase at room temperature, one can thus check the temperature independence of the barrier distribution function $`f(V)`$ (in that case, $`f(V)=f_s(V)`$) by a comparison between a torsion pendulum and a neutron or Raman experiment. Naturally, the same can be done by a comparison of a torsion pendulum and a Brillouin scattering experiment.

If one wants to determine the barrier distribution function from the mechanical damping for different frequencies, one often has to compare measurements of different elastic constants. A torsion pendulum measurement provides immediately the real and imaginary part of the shear modulus $`G`$. The vibrating reed technique measures Youngs modulus $`Y`$. In terms of the bulk modulus $`B`$, the inverse of the compressibility, Youngs modulus reads

$$Y=\frac{9BG}{3B+G}.$$
(45)
Since that quotient is close to $`3G`$, it is a reasonable approximation to identify the $`\mathrm{tan}\delta =G^{}/G\mathrm{"}`$ results of the vibrating reed technique (in that technique often denoted as $`Q^1=\mathrm{tan}\delta `$) with that of the shear modulus. The real part of the shear modulus can then be estimated to be $`Y^{}/3`$, or calculated accurately from the above equation if the bulk modulus is known.

A less safe connection is to longitudinal sound measurements, which determine the real and imaginary part of the elastic constant $`c_{11}`$, sometimes also denoted as the modulus $`M`$. In terms of $`B`$ and $`G`$, $`c_{11}`$ reads

$$c_{11}=B+\frac{4}{3}G.$$
(46)
Both contributions are of comparable size. Therefore, if one wants to determine $`\mathrm{tan}\delta `$ for the shear modulus from longitudinal sound attenuation data, one has to know the relative size of the two damping contributions from compression and from shear. Here it should be noted that the mechanical damping at very low temperatures is quite similar for transverse and longitudinal phonons in many glasses . If one believes the soft potential hypothesis for a common origin of tunneling states and low barrier relaxation in glasses, the same should hold in the temperature range up to 50 K. Then one can take $`\mathrm{tan}\delta `$ from the inverse mean free path $`l^1`$ of the longitudinal sound wave according to

$$\mathrm{tan}\delta =\frac{vl^1}{2\omega },$$
(47)
where $`v`$ is the sound velocity.

It is better to use data from transverse sound waves; there, the damping relates directly to the shear. However, in particular for light scattering Brillouin experiments, it is much easier to determine the damping for the longitudinal waves, which provide a much clearer signal. That damping is often given in terms of the half width at half maximum $`\mathrm{\Gamma }`$ of the Brillouin line. Then

$$\mathrm{tan}\delta =\frac{\mathrm{\Gamma }}{2\omega },$$
(48)
where $`\omega `$ is the frequency of the Brillouin line.

Finally, one problem of the determination of $`f(V)`$ is to know $`G`$ at the temperature of the measurement; usually one has only $`G^{}`$ and $`G\mathrm{"}`$. A way out of this problem is to start at low temperatures, where $`GG^{}`$, determine $`f(V)`$ via eq. (27), and then pursue $`G^{}/G`$ to higher temperatures via eq. (26). This way was followed throughout in this paper, at least as far as the determination of the secondary relaxation was concerned (the primary relaxation is too sharp to use the crude approximation of eq. (27); there, one has to use the exact equations).

One can try to check the $`G(T)`$ values by Brillouin light scattering measurements of the transverse sound waves, usually at frequencies around 10 GHz. Even there, one has to reckon with some influence from the low-barrier part of the relaxations; this is, however, only a small correction which can be easily done if one has $`f(V)`$, using eq. (26).

### B Polystyrene: secondary relaxation

We begin the comparison to experiment with a heavily studied glass former, atactic polystyrene, one of the most fragile substances , an amorphous polymer where one can rely on a large number of experimental data, both at low temperatures and at the glass transition.

The low temperature data were evaluated for temperatures above 10 K; at that limiting temperature, one can begin to reckon with the validity of the Kramers picture . Fig. 3 shows a compilation of many mechanical low temperature data: torsion pendulum data at 1 Hz , at 6 Hz , vibrating reed data at 3, 34 and 87 kHz  and Brillouin damping of longitudinal sound waves at 10 GHz . The data cannot be said to coincide perfectly in this Gilroy-Phillips evaluation; nevertheless, the agreement is fair enough to support the concept of a constant number density of uncoupled relaxation centers. There is no systematic variation with frequency; one rather has the impression that the differences stem from the different sample preparation of these seven measurements. The line in Fig. 3 represents the fit of $`f_s(V)`$ to these mechanical data. It is seen that $`f_s(V)`$ rises towards low barriers, as one would expect from the soft potential equation (43). But the fit line falls below the soft potential expectation already at rather low barriers, similar to observations in other glasses .

Fig. 4 compares the same fit to the evaluation of Raman  and neutron  data in terms of eq. (41). In the Raman case, data were adapted by an appropriate multiplication factor. The neutron data were evaluated using eq. (44) and the soft potential fit parameters of polystyrene , without any free parameter. The fit of the neutron data requires a good description of the vibrational part of the scattering; details will be given in a forthcoming publication combining time-of-flight and backscattering data of polystyrene .

The good agreement between data points and the mechanical data fit line in Fig. 4 corroborates the earlier conclusion  of a temperature-independent $`f_s(V)`$ in the glass phase of polystyrene. Note that the earlier conclusion does not stem from a comparison of Raman and mechanical data, but rather from a comparison of Raman data at three different temperatures, namely 100, 200 and 300 K. The two different ways to check the temperature behaviour of $`f_s(V)`$ in the glass phase provide the same result.

This temperature-independence, however, does no longer hold in the undercooled liquid phase, above the glass temperature of 372 K of polystyrene. Fig. 5 shows neutron  and longitudinal sound wave damping data from the Brillouin technique  above $`T_g`$. In order to relate to the preceding figures, $`f(V)`$ is again plotted against the barrier height $`V`$. This implies that one sees the onset of the increase of $`f_s(V)`$ with increasing temperature at different values of $`V`$ in the two techniques, at 0.074 eV for the neutrons and at 0.163 eV for the Brillouin data. Note that in both cases the frequency is too high to see the $`\alpha `$-process at the temperatures of the measurement.

We conclude that $`f_s(V)`$ does indeed increase above $`T_g`$, as postulated above on the basis of the sum rule for $`f(V)`$, eq. (15), and on the basis of the temperature dependence of the $`\alpha `$-process. The rise of $`f_s(V)`$ above $`T_g`$ can be characterized by the linear relation eq. (31) with $`\alpha _s=7.7\pm 1`$ for the neutron data and $`\alpha _s=10\pm 3`$ for the Brillouin data (in the latter case, the large error is due to the small number of points and the insecurity of the value at $`T_g`$), within experimental error the same temperature coefficient for both sets of data.

Fig. 6 shows $`f_s(V)`$ for polystyrene over the whole barrier range, together with the results of a torsion pendulum measurement at 1 Hz up to $`T_g`$ , an ultrasonic measurement just below $`T_g`$  and the neutron result up to $`T_g`$ . The shaded area represents $`f_s(V)`$; the $`\alpha `$-peak above 1 eV will be discussed in the next subsection.

### C Polystyrene: glass transition

The $`\alpha `$-process is characterized by the position $`V_\alpha (T)`$, the full width at half maximum $`\mathrm{\Delta }_\alpha `$ of $`f_\alpha (V)`$ and the weight $`w_\alpha `$. The latter two should be temperature-independent. Let us define $`V_\alpha (T_g)=15k_BT_g\mathrm{ln}(10)`$ in order to have the corresponding relaxation time at 100 s, and let us choose a gaussian for the primary barrier distribution function $`f_\alpha (V)`$.

If one knows $`f_s(V)`$ from measurements in the glass phase, $`w_\alpha `$ can be calculated from the sum rule eq. (30). In the case of polystyrene, one finds $`w_\alpha =0.54`$ for the fit function in Fig. 6.

The width $`\mathrm{\Delta }_\alpha =0.107`$ eV, the glass temperature $`T_g=372K`$ and the coefficient $`\alpha _s=6.9\pm 0.1`$ was fitted to creep data  of polystyrene with a molecular weight of 600000 g/mol, data which are also treated in Ferry’s book  and which are shown in Fig. 7. The fit requires as an additional parameter the infinite frequency modulus $`G=1.69`$ GPa at 373.8 K. Together with the low temperature data and the known density variation of polystyrene with temperature , one calculates a Grüneisen $`\mathrm{\Gamma }_g=3.8`$ for $`G`$ in polystyrene. With this value, one can also calculate $`G`$ for higher temperatures. The creep function $`J(t)`$ is obtained by first calculating $`l(V)`$ via eq. (22), the viscosity from eq. (19) and finally $`J(t)`$ from eq. (17).

As seen in Fig. 7, one can describe the temperature shift of the $`\alpha `$-process with an appropriate rise of $`f_s(V)`$ above $`T_g`$. The sum rule eq. (30) forces a temperature shift of $`V_\alpha (T)`$, which in turn provides the experimentally observed shift factors towards higher temperatures.

The scheme works quite well up to three decades in compliance; for still higher compliances, one gets into the plateau regime from the chain entanglement , which is beyond the present considerations.

### D Vitreous silica and sodium silicate

Vitreous silica is the case for which the Gilroy-Phillips idea  was originally developed. The compatibility between mechanical relaxation around 20 K and inelastic neutron scattering at room temperature was demonstrated seven years later . A very recent Raman experiment  showed the temperature independence of $`f_s(V)`$ up to room temperature, together with an excellent agreement of the shape of the function from mechanical data with the one from Raman data.

Of the many low-barrier mechanical data in the literature, we include here merely one of the Brillouin damping experiments at 35 GHz . The range of higher barriers is covered by a torsion pendulum measurement  and a mHz experiment at the glass transition itself . Fig. 8 shows the barrier distribution function fitting these data over the whole range. Again, it turns out to be possible to fit the $`\alpha `$-relaxation in terms of a gaussian for the primary barrier distribution function $`f_\alpha (V)`$, ascribing the slow rise of the damping towards the glass transition to secondary relaxation (the shaded area in Fig. 8).

Fig. 9 shows the fit of the glass transition data , calculated with $`T_g=1460`$ K, $`G=31`$GPa, $`w_\alpha =0.55`$ and $`\mathrm{\Delta }_\alpha =0.263`$eV. If one takes the value $`T_gT_0=850`$K and its rather large error bars from the shift factors determined in , one calculates $`\alpha _s=6\pm 4`$ from eq. (33).

It is interesting to compare vitreous silica to a sodium silicate glass, Na<sub>2</sub>O:2SiO<sub>2</sub>, which has a much lower glass temperature $`T_g=733`$K and is much more fragile , with $`T_gT_0=267`$K. Fig. 10 shows the barrier distribution function, together with torsion pendulum data  at 0.4 Hz. The $`\alpha `$-peak region is again fitted to the mHz data , shown in Fig. 11, with $`G=19`$GPa, $`w_\alpha =0.39`$ and $`\mathrm{\Delta }_\alpha =0.092`$eV. The shift factors  require $`\alpha _s=13\pm 1.5`$.

## IV Results and discussion

### A Results for the flow process

The preceding section showed for all three examples a good fit of the $`\alpha `$-relaxation in terms of a narrow gaussian primary barrier distribution function, together with a bigger or smaller contribution of the secondary relaxation. The contribution of the secondary relaxation to the $`\alpha `$-process was biggest in the strong glass former silica and smallest in the very fragile case of polystyrene. In all three cases, excellent fits of the time or frequency dependence of the $`\alpha `$-process could be obtained (see Figs. 7, 9 and 11). Simultaneously, the temperature dependence of the shift factors for $`\tau _\alpha `$ could be described accurately by the temperature slope $`\alpha _s`$ of the rise of the secondary relaxation above $`T_g`$ in eq. (31).

Table I compiles the fit parameters for the $`\alpha `$-process determined in the preceding section.

Table I: Model parameters for the $`\alpha `$-process

| substance | polystyrene | SiO<sub>2</sub> | Na<sub>2</sub>O:2SiO<sub>2</sub> |
| --- | --- | --- | --- |
| $`T_g`$ (K) | 372 | 1460 | 733 |
| $`G(T_g)`$ (GPa) | 1.69 | 31 | 19 |
| $`w_\alpha `$ | 0.54 | 0.54 | 0.39 |
| $`\mathrm{\Delta }_\alpha `$ (eV) | 0.107 | 0.263 | 0.092 |
| $`\alpha _s`$ | 6.9$`\pm `$0.1 | 6$`\pm `$4 | 13$`\pm `$1.5 |

In all three cases, the relative weight $`w_\alpha `$ of the $`\alpha `$-process is not very far from 1/2. The $`\alpha `$-process seems to occur when the secondary relaxations reduce the shear modulus to about half its infinite frequency value, i.e. when the secondary relaxational shear response equals the elastic one. The situation reminds one of the definition of the Maxwell time $`\tau _M=\eta _0/G`$, the time when the flow response equals the elastic one. Thus one could think of a generalized Maxwell criterion for the onset of the flow process, namely when the shear response by relaxation is the same as the elastic shear response. Intuitively, this is plausible: the time at which a macroscopic shear stress for a given strain decays to half its initial value should correspond to the lifetime of the microscopic shear pattern of the glass former, because the microscopic stresses will be expected to decay on the same time scale as the macroscopic ones. But a decay of the microscopic stresses necessarily implies a coupling between different relaxation centers in the glass. Thus one would have to go beyond the simple idea of uncoupled relaxation centers to understand the flow process .

In all three cases, the width $`\mathrm{\Delta }_\alpha `$ is relatively narrow, less than one tenth of the barrier $`V_\alpha (T_g)`$ itself, in the third case even less than the twentieth part.

Finally, the coefficient $`\alpha _s`$ for the temperature rise of the secondary barrier distribution function $`f_s(V)`$ above $`T_g`$, related to the fragility of the glass former, is not so very different for the three cases. There is a factor of two between silica and the silicate glass, but taking the differences in the glass temperature into account, one sees that the relative rise per Kelvin is the same for the two glasses, admittedly within large error bars. The difference is rather in $`f_s(V)`$ itself; obviously, relaxing entities form much more easily and with much lower barriers in the multiply broken network of the sodium silicate glass than in the continuous random network of silica, making the glass temperature a factor of two lower.

The large difference in fragility between silica and polystyrene is not so much due to a difference in $`\alpha _s`$, but rather in the product $`Vf_s(V)`$ at $`T_g`$ (see Figures 6 and 8), which is about 0.3 in polystyrene and about 2.5 in silica. This product enters into eq. (33) for the Vogel-Fulcher temperature $`T_0`$. In this view, a substance is fragile when it has a low density of secondary relaxing entities at the relaxation time of the flow process. Naturally, the fast rise of the number of secondary relaxing entities above $`T_g`$ remains a necessary condition.

The coefficient $`\alpha _s=6.9\pm 0.1`$ for polystyrene in Table I, obtained from the temperature dependence of the shift factors (see Fig. 7), agrees within experimental error with the values $`\alpha _s=7.7\pm 1`$ and $`\alpha _s=10\pm 3`$ determined from neutron and Brillouin data above $`T_g`$ (see Fig. 5).

### B Discussion

Here is the proper place to remind the reader that with all the presented equations and fits, the glass transition is not really explained. The Gilroy-Phillips formalism supplies only a reformulation of well-known equations in terms of a barrier distribution function. It is a new way to look at the data, an encouragement to seek explanations in a new direction, complementary to attempts to understand the glass transition from the liquid side , because it starts from a description of the relaxation in the glass phase. But the present work does neither explain the fast rise of the secondary relaxation above $`T_g`$, nor does it supply a quantitative explanation why the shear modulus breaks down completely when it is halved by the secondary relaxation. It merely helps to quantify and to visualize these experimental facts.

The concept of the barrier distribution function is based on the idea of independent thermally activated relaxation processes in disordered surroundings. As long as this idea applies without any restriction, one should find a temperature-independent barrier distribution function, as one does indeed in the glass phase of polystyrene and silica. The quantitative comparison of measurements at different temperatures and frequencies with the equations of Section II.C enables a much more stringent check of the Arrhenius concept than a mere Arrhenius temperature shift of a broad relaxation peak with frequency . From the few such stringent checks reported so far, it is already clear that the concept does not always work perfectly well in the glass phase. In BPA-PC, another amorphous polymer, there is Raman evidence  for an increase of the secondary barrier distribution function $`f_s(V)`$ with temperature below $`T_g`$ , even though the $`\gamma `$-relaxation peak shift is perfectly Arrhenius-like . There seem to be more such cases . This is yet another question calling for a closer investigation.

The outcome of the fits of the flow process in terms of the primary barrier distribution function $`f_\alpha (V)`$ shows once more the collectivity of the flow process. These are clearly not independent thermally activated relaxation processes; otherwise $`V_\alpha `$ would not shift with temperature. There has been an attempt  to explain the temperature dependence of $`V_\alpha (T)`$ in terms of a proportionality to $`G(T)`$ (”flow by shoving”). However, as pointed out in Section III.C, one finds a Grüneisen $`\mathrm{\Gamma }_g=3.8`$ for $`G(T)`$ in polystyrene. This is a factor of seven too weak to explain the temperature shift of $`V_\alpha (T)`$.

In any case, the description of the flow process in terms of $`f_\alpha (V)`$ in principle does not prejudice anything. One can always return from $`f_\alpha (V)`$ to the conventional description  in terms of $`H(\tau )`$ via eq. (11). What might be questionable is the specific subdivision into primary and secondary relaxation. Here, it was decided to fit the primary barrier distribution function $`f_\alpha (V)`$ with a gaussian. On the basis of the data, this choice can be only justified for polystyrene; in the other two cases, one could choose differently. The conclusion that the shear modulus is reduced to about half its infinite frequency value by the secondary relaxation alone would then no longer be valid for these two cases.

Independent of the choice of a specific function for the primary barrier distribution function, the new description is much more convenient than the old one if one wants to compare different temperatures. It does not only allow for a stringent check of the Arrhenius behaviour in the glass phase, but it also holds the promise to provide a deeper understanding of the glass transition riddles . As shown in Section II.E, the stretching of the flow process is quantitatively related to the width of the $`\alpha `$-peak. More important, the Vogel-Fulcher behavior is an inherent feature of the generic case of a constant secondary barrier distribution function, provided it has a constant temperature rise. But one can as well understand deviations  from the Vogel-Fulcher behavior in terms of maxima and minima of the secondary barrier distribution function. In particular, one must expect deviations from a single Vogel-Fulcher law when $`V_\alpha (T)`$ sweeps through a secondary relaxation peak, as one indeed observes .

## V Summary and conclusions

The Gilroy-Phillips model  for secondary relaxation in glasses, based on the Arrhenius-Kramers  picture of thermally activated jumps over energy barriers, has been extended to describe the flow process (primary or $`\alpha `$-process). The proper treatment of uncoupled thermally activated relaxation events in disordered surroundings yields a temperature-independent barrier distribution function $`f(V)`$. The temperature independence holds as long as one has a constant number of independent relaxation centers. The function has to integrate to 1 in order to bring the shear modulus down to zero, a very convenient sum rule. As it turns out, one can use the formalism to describe any kind of relaxation, admitting a temperature dependence of the barrier distribution function. Thus one can separate the trivial Arrhenius temperature dependence from nontrivial temperature changes of the relaxation.

The relaxation below the glass temperature $`T_g`$, in the frozen energy landscape of the glass, should be describable in terms of a temperature-independent barrier distribution function (in some cases like polystyrene, CKN and silica  it works, in others it does not ), but the flow process is most certainly of a different kind. Therefore one has to postulate a secondary barrier distribution function $`f_s(V)`$ for the secondary relaxation, and an additional primary barrier distribution function $`f_\alpha (V)`$ for the flow process. This additional primary function shifts its maximum to lower values with increasing temperature and serves simultaneously as a relatively sharp cutoff for the secondary relaxation. This property supplies a quantitative basis for the puzzling relation between the fragility and the fast rise of the picosecond process above $`T_g`$ . It explains the unusual temperature dependence of the flow process in terms of the temperature rise of the secondary relaxation, and might even shed some light on the detailed temperature dependence of the flow process in specific substances .

Reformulating the classical rheological equations , experimental literature data in polystyrene, vitreous silica and a sodium silicate glass could be fitted in terms of the barrier distribution functions. The results corroborate the earlier conclusion  of a temperature-independent secondary barrier distribution function in the glass phase of polystyrene, but show a strong increase of the secondary relaxation with increasing temperature above $`T_g`$. Taking the flow process as a gaussian barrier distribution function, the fits show the onset of the flow process more or less at the point where the secondary relaxation reduces the shear modulus to half its infinite frequency value. This was not only found in polystyrene, but in the two other cases as well. It remains to be seen whether such a generalized Maxwell criterion for the onset of the flow process is a general property of glass formers. In polystyrene, the temperature coefficient of the fast rise of $`f_s(V)`$ above $`T_g`$ calculated from the fragility coincided within experimental error with the fast rise seen in neutron and Brillouin experiments.

The findings suggest a rapid change of the energy landscape above $`T_g`$, the landscape getting more and more rugged with more and more minima and saddle points as the temperature rises, thus also explaining the entropy crisis at the Kauzmann temperature. This does not really answer the central questions around the glass transition, but focusses the attention on two points: (i) what is the possible mechanism of formation of an increasing number of relaxing entities with increasing temperature above $`T_g`$ (ii) why does the flow process set in when the integrated relaxational response to an external shear stress equals the elastic one.

Acknowledgements: Helpful discussions with A. Wischnewski, E. W. Fischer and K. L. Ngai are gratefully acknowledged.

Figure Captions

Fig. 1: Asymmetric double well potential with barrier height $`V`$ and asymmetry $`\mathrm{\Delta }`$ as a function of a generalized coordinate.

Fig. 2: Secondary barrier distribution function $`f_s(V)`$ (the shaded area), together with the cutoff by the $`\alpha `$-relaxation peak (schematic).

Fig. 3: Secondary barrier distribution function $`f_s(V)`$ calculated from literature data of the mechanical damping of amorphous polystyrene in the glass phase at different frequencies. References see text. The line is a fit; the same fit is also shown in Figs. 4, 5 and 6.

Fig. 4: Secondary barrier distribution function $`f_s(V)`$ calculated from literature data of neutron and Raman scattering from amorphous polystyrene in the glass phase. References see text.

Fig. 5: Secondary barrier distribution function $`f_s(V)`$ calculated from literature data of neutron and Brillouin data of amorphous polystyrene, both in the glass phase and above the glass temperature $`T_g`$. References see text.

Fig. 6: Secondary barrier distribution function $`f_s(V)`$ calculated from literature mechanical damping and neutron data of amorphous polystyrene up to the glass transition. The peak at the end shows the gaussian $`f_\alpha (V)`$ describing the $`\alpha `$-process at the glass temperature $`T_g`$. References see text.

Fig. 7: Creep data of the $`\alpha `$-process in polystyrene at the glass transition (reference see text), together with a fit in terms of $`f(V)`$.

Fig. 8: The barrier distribution function of vitreous silica, together with torsion pendulum and Brillouin damping data. References see text.

Fig. 9: Dynamical mechanical data of vitreous silica at the glass transition, together with the model fit (see text).

Fig. 10: The barrier distribution function of Na<sub>2</sub>O:2SiO<sub>2</sub>, together with torsion pendulum data. References see text.

Fig. 11: Dynamical mechanical data of Na<sub>2</sub>O:2SiO<sub>2</sub> at the glass transition, together with the model fit (see text).


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# The Edinburgh/Durham Southern Galaxy Catalogue – IX. The Galaxy Catalogue

## 1 Introduction

Surveys of galaxies are invaluable tools for cosmologists. To date, the most comprehensive catalogues of galaxies have resulted from the optical photographic surveys carried out with the Schmidt telescopes at the Palomar and Anglo–Australian Observatories. The earliest of these surveys were visually compiled counts of galaxies, the largest being the Lick catalogue of galaxies which presents counts in cells of $`10\times 10`$ arcminutes for some 800,000 galaxies covering two thirds of the entire sky. The complementary Abell cluster catalogue (Abell, Corwin & Olowin 1989) is an amalgamation of Abell’s original northern cluster catalogue (Abell 1958), carried out with the Palomar Sky Survey 103a–E plates, with the southern extension using the IIIa-J Southern Sky Survey plates taken by the UK Schmidt at Siding Springs. The final all–sky Abell catalogue consists of 4073 rich clusters of galaxies each having at least 30 members with a nominal redshift of $`z0.2`$ and is the first serious attempt to systematically categorize the properties of galaxy clusters. The Abell catalogue remains the most widely used cluster catalogue in the astronomical literature.

The early 1990s saw the completion of the first large-scale digitized galaxy surveys. These combined the best available photographic material, in the form of UK Schmidt IIIa-J photographic survey plates, with digitization technology in the form of fast micro-densitometers e.g. the COSMOS machine in Edinburgh and the APM machine in Cambridge. The digitization process overcomes the inherent subjectivity of ‘eyeball’ surveys and the impact of the resulting galaxy catalogues has been extensive (see Section 3).

As we enter a new millennium, the number and size of galaxy surveys will expand rapidly due to new photographic galaxy surveys (e.g. DPOSS, Djorgovski et al. 1998; SuperCOSMOS, Phillipps et al. 1998) and CCD surveys (e.g. SDSS, York et al. 2000). These new surveys will supersede the presently available galaxy catalogues because of their increased sensitivity, areal coverage, color information and more accurate photometry. Therefore, in this paper, we announce the public release of the Edinburgh/Durham Southern Galaxy Catalogue (EDSGC) to assist cosmological research and is now particularly timely given the completion of several redshift galaxy surveys for which the EDSGC has been the input object catalogue (see Section 4).

The structure of this paper is as follows: In Section 2, we discuss the construction of the EDSGC and describe the available parameters and catalogue characteristics. In Section 3, we outline the availability of the EDSGC and in Section 4, we present a summary of the supplementary data available in the EDSGC area. In Section 5, we present the extensive external checks that have been performed on the catalogue, while in Section 6, we review the science which has been carried out using the EDSGC.

## 2 The Edinburgh/Durham Southern Galaxy Catalogue

The Edinburgh/Durham Southern Galaxy Catalogue (EDSGC) is one of the first fully automated objective galaxy catalogues to be constructed. It covers an area of $`1200\mathrm{d}\mathrm{e}\mathrm{g}^2`$ centered on the South Galactic Pole (SGP) and contains extensive information on over one million galaxies. The majority of the initial work involved in its construction has already been presented in several places i.e. Collins, Heydon-Dumbleton & MacGillivray 1989, Heydon-Dumbleton, Collins & MacGillivray 1989 and Heydon-Dumbleton 1989. In this section we summarize the data and the methods used in the catalogue’s construction and presents some of the tests implemented on the completed EDSGC.

### 2.1 The Raw Data

The UK Schmidt Telescope (UKST) at Siding Springs in Australia was commissioned in late 1973 to carry out a systematic photographic survey of the southern hemisphere. The UKST has a 1.8m diameter mirror with a 1.2m aperture which provides a large field of view making it ideal for the construction of such a large-area survey. The photographic plates used by UKST subtends an area of $`6.4^{}\times 6.4^{}`$ on the sky with a plate scale of 67.12 arcseconds per millimeter. For all the surveys carried out by UKST, the centers of the plates are separated by $`5^{}`$ which provides a substantial overlap between them and removes the need to use the plate edges which are heavily vignetted (vignetting is negligible within $`2.7^{}`$ of the plate center).

The EDSGC is based on plates taken from the ESO/SERC Atlas. This atlas consists of glass copies of the SERC J survey which was the first survey to be completed by UKST and covers the whole southern sky below a declination of $`17^{}`$ (606 plates in total). The passband of the SERC J survey is defined by the response of the emulsion (Kodak IIIA-J) combined with a Schott GG395 filter. This provides an almost uniform sensitivity in the wavelength range $`3500\AA `$ to $`5400\AA `$ and is close to the standard Kron-Cousins B passband. Image magnitudes on the plates are usually referred to as $`b_j`$ magnitudes.

Both the original J survey plates and the atlas copies were taken using a strict set of criteria to minimize systematic errors between different plate exposures and, more importantly, to ensure that the process was highly repeatable. For example, survey plates were only taken in dark time, good seeing (less that 3 arcseconds) and with the sun $`>18^{}`$ below the horizon to avoid astronomical twilight. During the exposure, each plate was held in a curved holder and was flushed with nitrogen to reduce the effects of differential desensitisation over the plate111We note here that a few EDSGC plates may have been taken before nitrogen–flushing was instigated. The developing and copying of the plates were also carried out with a high degree of consistency to ensure that systematic differences between plates were not introduced. Finally, quality control checks were carried out on all plates and each was graded either A, B or C. Therefore, this atlas represented the most homogeneous catalogue of photographic plates available at that time. The reader is referred to the UK Schmidt Telescope Unit Handbook (1983) for a description of the procedures used in taking the original plates, Cannon et al. (1978) for full details of the processing of the plates and Bruck & Waldron (1984) for a discussion of the copying process.

In total, 60 grade A plates were used in the EDSGC and these are listed in Collins, Nichol & Lumsden (1992; CNL92). These plates were extracted from the ESO/SERC Atlas held in the UK Schmidt Library at the Royal Observatory Edinburgh and scanned by COSMOS, also at the Royal Observatory Edinburgh. The COSMOS machine was a high-speed flying spot micro–densitometer, specifically designed and constructed for scanning astronomical photographic plates (details of COSMOS can be found in MacGillivray & Stobie (1984) while the characteristics of its descendent, SuperCOSMOS, are to be found in Miller et al. 1991) . The COSMOS machine originally sat on a plinth driven 35 feet into the ground which separates it from the rest of the building thus preventing vibrations of any sort from effecting the scans. In addition, COSMOS and the UKST plate library were kept in a dust-free environment, thus reducing the chances of contamination on the plates.

Plates were fed into COSMOS with their south side at the top of the plate carriage holder and raster scanned using a beam of light from a cathode ray tube of width 8 microns. As the plate moved in the y direction, the beam scans in the x direction with a pixel size of 16 microns. In total, an area of $`287\mathrm{m}\mathrm{m}\times 287\mathrm{m}\mathrm{m}`$ was scanned each time which corresponds to an area of $`5.35^{}\times 5.35^{}`$ on the sky. For each pixel, a transmission value was calculated by comparing the light measured passing through the plate with a reference signal. This in turn, was converted into a measured intensity using a Baker density calibration curve (MacGillivray & Stobie 1984).

COSMOS was operated in two modes; mapping and threshold. The first recorded all the pixel information on a plate and therefore required a vast amount of computer storage. The second recorded only pixels that were a certain percentage above the sky background of the plate (the typical sky background for these plates is $`22.3`$ magnitude per square arcsecond in the photographic $`b_j`$ system). This is determined beforehand by scanning the plate with a much lower resolution (32 microns) to measure the large scale variations over the plate which are usually due to a combination of large nearby stars, vignetting and differential desensitisation. After scanning, the pixel data was passed into the COSMOS image analyzer (see Beard, MacGillivray & Thanisch 1990) which connects all adjacent pixels producing a final set of objects for each plate. Each image was then assigned 27 individual image parameters such as the image magnitude, position and both the intensity weighted and unweighted moments of the pixel distribution (Stobie 1980 and Section 3 below). Plates used in the EDSGC were scanned in threshold mode, with a threshold of 8% to 10% above the sky background. This ensured that there were approximately the same number of objects in each scan and was found by MacGillivray & Dodds (1982) to be an acceptable level for maximizing the number of true images compared to ‘noise’ images.

The magnitudes returned by COSMOS were isophotal magnitudes and the threshold quoted above for the EDSGC corresponded to a final isophote of 25 magnitudes per square arcsecond in $`b_j`$. For images brighter than $`b_j=20.5`$, the magnitudes were effectively total magnitudes (MacGillivray & Dodds 1982). In addition, the measured magnitudes depend upon the sky background magnitude of the scanned plate and adopting a fixed detection threshold for all the plates introduced large variations between the zero-point magnitudes of the plates. Therefore, it was imperative to obtain external photometry to calibrate the magnitude scale of each plate.

All the COSMOS scans used in the EDSGC were analyzed using the COSMOS de-blending software (Beard et al. 1990), which involved re-thresholding each image in intensity space at 8 progressively higher thresholds in search of saddle-points in the image’s intensity distribution. If such saddle-points were found, the separate peaks were fitted by Gaussians and split into their daughter images. At the SGP, the number of blended objects was found to be $`10\%`$ at all magnitudes and implementing the de-blending software substantially reduced this number e.g. at a surface density of 20 galaxies per square arcminute (e.g. the cores of rich clusters) the number of real objects detected increased by over 30% because of de-blending (Heydon-Dumbleton et al. 1989). De-blending of the images was vital to the EDSGC for two reasons. First, faint star-star mergers near the plate limit imitated galaxies because their combined shape appeared elliptical and they had a lower surface brightness compared to a single star. If these were not de-blended, then there would have been a significant contamination of false galaxies at faint magnitudes. Secondly, the EDSGC was used in the construction of an automated cluster catalogue (Section 6). If de-blending had not been implemented, the cores of many rich clusters would have appeared as single large objects and therefore, would not have been detected by the automated cluster detection algorithm.

#### 2.1.1 Star-Galaxy Classification

A detailed discussion of the COSMOS star-galaxy separation criteria can be found in Heydon–Dumbleton et al. (1989). However, for completeness, we given an overview of the techniques here.

A COSMOS scan of a typical Schmidt plate contains on average 200,000 objects. To the plate limit, over 90% of these objects are stars which clearly must be removed to produce a reliable and meaningful galaxy catalogue. For the EDSGC, this was achieved using 3 parameters defined during the scanning of the plates. Each parameter worked over a different magnitude range and their combined effect covered the full range of magnitudes observed on a plate.

These 3 classifiers were: The G classifier which works for magnitudes brighter that $`b_j16`$ and effectively measures how well an object fills the ellipse fitted to it (for stars brighter than $`b_j16`$, diffraction spikes dominate the fitted ellipse but they have a relatively small area, while galaxies at this magnitude tend to fill their fitted ellipse): The Log-area classifier which works at intermediate magnitudes ($`16<b_j<19.5`$) and relies on the fact that galaxies have a lower surface brightness than stars: The S classifier which works for magnitudes fainter than $`b_j=19.5`$ by comparing the measured size of the image to that expected for a Gaussian point–spread function.

Near the limit of the plates, star–galaxy separation became extremely difficult. Therefore, COSMOS scans used in the EDSGC were cut at a COSMOS magnitude of -1.0, which roughly corresponded to $`b_j21`$ for most plates. To test the reliability of the star-galaxy separation, visual checks were carried out on 5 plates spread across the EDSGC. For each plate, 300 classified galaxies and 300 classified stars, over a broad range in magnitude, were randomly selected and visually inspected. The result of this test was a $`>95`$% completeness for the galaxies at all magnitudes with $`<10`$% stellar contamination. Similar results were obtained for visual checks on images selected before and after de-blending. For a much fuller discussion of these classifiers, their effective magnitude ranges and the visual tests the reader is referred to either Heydon-Dumbleton et al. (1989) or Heydon-Dumbleton (1989).

#### 2.1.2 Photometric Calibration

As stated above, COSMOS only returned the magnitude of objects relative to the background magnitude limit of the plate. Therefore, it was essential to obtain external photometry to calibrate all the galaxies in the EDSGC by determining the sky background magnitude or zero-point magnitude of the plates. For galaxies, the relationship between the COSMOS magnitude and the $`b_j`$ magnitude is linear over a wide range of magnitudes and can be represented by $`b_j=m_{cosmos}+m_{sky}`$ where $`m_{cosmos}`$ is the instrumental magnitude (and negative) and $`m_{sky}`$ is the constant sky background of the plate (see below and Table 1).

The EDSGC was calibrated using CCD direct images obtained at CTIO and SAAO. In total, 31 calibration sequences were taken across the whole EDSGC and were spaced in a “checker board” fashion i.e. plates either had a sequences on them or overlapped with two or more plates with a sequence on. Each CCD frame was centered on a loose cluster which resulted in $`15`$ usable galaxies per frame for the calibration. For the plates with a sequence, the COSMOS magnitudes of the observed galaxies were plotted against their CCD magnitudes and from the fit (with the slope fixed at 1.0) $`m_{sky}`$ was obtained. These zero-points were then used to calibrate the whole of the plate with a uncertainty of $`0.05`$ magnitudes. In Table 1, we present our measured $`m_{sky}`$ values for the 31 EDSGC plates with a CCD sequence. Plates marked with an asterix have an uncertain calibration and should be viewed as preliminary at present. For plates without a sequence, $`m_{sky}`$ was calculated using the galaxies in the overlap regions with plates with a sequence (typically 1000-3000 galaxies in each overlap). On average, each uncalibrated plate overlapped with 2-3 calibrated plates which prevented erroneous calibrations from propagating through the survey (see our discussion of edge plates below).

The histogram of measured plate magnitude offsets between adjacent plate zero–points is presented in CNL92 and the best fit Gaussian to this distribution has a dispersion of 0.08 magnitudes. This implies a calibration uncertainty of 0.05 magnitudes on each plate which is within the limits set by Geller, Kurtz & de Lapparent (1984) for plate matching errors for any new galaxy catalogue used in measuring the large scale distribution of galaxies. Once again, the reader is referred to Heydon-Dumbleton (1989) and Nichol & Collins (1993) for a more detailed description of the photometric calibration of the EDSGC and a fuller discussion of the errors.

### 2.2 Final Catalogue

#### 2.2.1 Spurious Detections and Systematic Errors

Before the plates were joined to form one homogeneous catalogue, the individual COSMOS scans were cleaned of spurious objects. The main source of such objects was from the accidental de-blending of star halos around bright stars in the field ($`b_j<12`$) which tended to mimic rich clusters of galaxies. To combat this effect, the areas around stars brighter than $`m_{cosmos}=9`$ were removed or “drilled” with a radius of 6.7 arcminutes (UKST handbook 1983). The exact magnitude used to select the stars was obtained from the plots of the G parameter against magnitude. In total, 553 such “drill holes” were made and a full list of these holes can be found on the EDSGC webpage.

Other spurious objects were produced by ghosts from very bright stars ($`b_j6`$) in the field, satellite trails, large nearby galaxies and dense star clusters. Therefore, we plotted the galaxy distribution on each plate and visually inspected these plots for any suspicious features (e.g. very dense clusters of galaxies etc.). Such features were then inspected on the original glass plates to determine if they were real astronomical objects or errors as discussed above. If they were spurious, the data around these objects was interactively removed from the catalogue. In particular, Fields 404, 356 & 469 had large star ghosts which were drilled with a radius of 40 arcminutes and Field 466 had a large de-focussed region in the northwest corner of the plate. This area was removed as no alternative plate existed with a comparable overall quality. In total, 10 interactive drill holes were used in the EDSGC and their positions, with comments, are given in Table 2.

Another source of contamination in the catalogue came from satellite trails. From the visual checks of the galaxy distribution of the plates, 11 plates were found to have this form of contamination. Combined with this, there were also spurious galaxies associated with the de-blending of diffraction spikes of stars. Both these types of spurious image were removed using the fact that they had preferentially aligned position angles i.e. diffraction spikes of stars were aligned with the edges of the plate and therefore, their position angles were always $`0^{}`$, $`90^{}`$ or $`180^{}`$. In addition, these images have high ellipticities and filled their fitted ellipse extremely well. Therefore, on the plates in question, all detected objects were plotted in the eccentricity (minor over major axis) versus position angle plane which cleanly separated the satellite trails from the majority of other objects. A cut was made in eccentricity (typically between 0.3 and 0.4) and all objects with a lower value than this cut were plotted in the log–area versus magnitude plane (i.e. as used for star–galaxy separation). As discussed above, the real galaxy population stood away from the spurious population and the two were separated simply using a straight line. This method was very effective at removing the satellite trails and diffraction spikes, with typically 500 images removed on each plate. As a check, the objects both rejected and re-accepted into the catalogue by this methodology were visually inspected on 5 of the 11 affected plates. Of rejected images, $`8\%`$ were galaxies, while for the re–accepted images, over 95% were galaxies. Due to the success of this method in removing residual diffraction spikes, it was performed on all the plates in the EDSGC and on average $`100`$ objects were removed per plate. Visual checks of these rejected objects were in agreement with the numbers quoted above.

Once all the plates had been photometrically calibrated and cleaned of spurious objects, the individual COSMOS scans were mosaiced together to produce a final homogeneous catalogue of galaxies. This was achieved interactively because the extent of the overlap between different pairs of plates varied extensively. The western edges of the UK Schmidt plates suffered the worst vignetting and desensitisation (UKST handbook 1983), while the northern edges displayed a systematic excess of faint galaxies which seemed to be a problem with the COSMOS calculation of the plate background intensity near that edge. This systematic excess was not due to the image classification or the photometric calibration because the effect was still present in the raw COSMOS scans (however, we note it only effected the first few lanes of the COSMOS scan and was therefore, only effected a small area of the plate). The EDSGC plates were attached together with a preference towards the eastern edges of the plates into long strips of fixed declination, which were then added together with a preference given towards the southern edges of these strips.

#### 2.2.2 Areal Coverage

The EDSGC contains 1,495,877 galaxies taken from 60 Schmidt survey fields as listed in Table 2 of CNL92. The largest contiguous region within the EDSGC (avoiding the complicated plate boundaries of the EDSGC) is given by: $`3^{hrs}`$ to $`22^{hrs}`$ (through $`0^{hrs}`$) and $`23^{}`$ to $`42^{}`$ (B1950). This gives a total area of $`1182\mathrm{d}\mathrm{e}\mathrm{g}^2`$ and should be used as the EDSGC window function i.e. we recommend users confine themselves to this region for all statistical analyses. This was the region used by CNL92 for the galaxy angular correlation function.

## 3 Availability of the EDSGC

The EDSGC is available for download over the internet from http://www.edsgc.org. On this webpage, there are two catalogue available: The first is a smaller version of the EDSGC with only 7 attributes (see Table 3) and the full EDSGC with 27 attributes (see Table 4). In Tables 3 and 4, column 1 gives the name of the attribute, Column 2 gives the units of the attribute and Column 3 is a short description of the attribute. It is worth re-iterating here that the plate scale of the UK Schmidt Telescope is 67.12 arcseconds per millimeter giving 1.07 arcseconds per COSMOS pixel. These numbers will allow users of the EDSGC to convert some of the catalogue attributes into astronomically meaningful values.

## 4 Supplementary Information on the EDSGC

Over the past decade, there has been significant auxiliary information gathered in the EDSGC area. Such data includes the Las Campanas Redshift Survey (LCRS; Shectman et al. 1996), the ESO Nearby Abell Cluster Survey (ENACS; Katgert et al. 1996), the ESO Slice Project (ESP; Vettolani et al. 1997) and the Durham/UKST Redshift Survey (DURS; Ratcliffe et al. 1998). The former two surveys provide serendipitous information while the latter two redshift surveys use the EDSGC, or a subset of the survey, as their input catalogues. In total, there are 12,888 EDSGC unique galaxy redshifts from these four surveys (5996 from LCRS, 3836 from ESP, 2501 from DURS and 907 from ENACS) and we make these data available on the main EDSGC webpage (see http://www.edsgc.org). Only 176 EDSGC galaxies have more than one redshift measurement from these four different redshift surveys and, for these galaxies, the mean absolute difference in redshift is $`71\mathrm{k}\mathrm{m}\mathrm{s}^1`$ (the largest observed difference is $`306\mathrm{k}\mathrm{m}\mathrm{s}^1`$).

## 5 External Checks

### 5.1 Photometry

Extensive checks of the internal photometric calibration of the EDSGC were carried out in Heydon-Dumbleton (1989). These checks centered around the examination of galaxies in the overlap regions of plates and on the galaxy number counts as a function of right ascension and galactic latitude. These internal tests showed no evidence for systematic calibration errors in the EDSGC.

In this section, we investigate external checks of the EDSGC photometry since as demonstrated in Nichol & Collins (1993) systematic plate–to–plate photometric errors can significantly affect the form of the galaxy angular correlation function (see CNL92). Therefore, it is important to have a homogeneous magnitude system across the whole EDSGC.

#### 5.1.1 External $`b_j`$ CCD data

In Nichol (1993), we presented two external checks of the EDSGC photometry. The first of these used the published CCD photometric calibration sequences of the APM galaxy survey (Maddox, Efstathiou & Sutherland 1990a). At the bright end ($`b_j<17`$), the scatter in magnitude is large with a typical difference between the two surveys of $`\pm 0.2`$ magnitudes. However, the majority of the comparison data are for galaxies fainter than a mean magnitude of $`b_j=18`$. Over a range of 3 magnitudes, the data are consistent with the expected scatter due to the APM & COSMOS machine measuring errors ($`0.1`$ magnitudes). The main result of this comparison is an overall 0.2 magnitude shift at all magnitudes between these two independent surveys, with the APM being the fainter of the two. A large part of this discrepancy could be the difference between total (APM) and isophotal (EDSGC) magnitude measurements

In terms of the correlation analysis presented in CNL92, a simple shift in the global magnitude calibration between the APM and COSMOS catalogues is not a significant problem, since the angular correlation function is scaled by the observed number density of galaxies in the catalogue. A potentially more serious problem would be the existence of a variable magnitude shift as a function of plate position or right ascension, as this would introduce large scale gradients. To test for this, the mean magnitude shift of EDSGC plates with an APM sequence were investigated as a function of Right Ascension. As discussed in Nichol (1993), this analysis showed no signs of a systematic variation in the 0.2 magnitude shift between the two surveys across the whole EDSGC survey. This is supported by a linear fit to the data, which gives $`\mathrm{\Delta }m_{APMCOSMOS}=(0.18\pm 0.04)(1.6\pm 2.8)\times 10^2\alpha `$, where $`\alpha `$ is the right ascension of the EDSGC plate center (24 hours was subtracted for RA coordinates greater than 12 hours). This relationship predicts an offset of only 0.07 magnitudes between the two ends of the EDSGC, with a one sigma upper offset limit of 0.21 magnitudes.

In addition to the APM CCD sequences, Nichol (1993) used two CCD calibration sequences used by Matthew Colless in his study of the cluster luminosity function (Colless 1986). This comparison however does not show any systematic displacement between the EDSGC and Colless zero–points and is fully consistent with the expected scatter about zero given the COSMOS machine measuring error. In addition, the two Colless sequences (on Fields 349 and 405) are separated by nearly 2 hours in right ascension and show no evidence for a systematic shift in the EDSGC magnitude zero–points.

#### 5.1.2 Other External Photometry Data

As outlined in Section 4, there are 5996 galaxies in common between the Las Campanas Redshift Survey (LCRS; Shectman et al. 1996) and the EDSGC. These galaxies were matched using a search radius of 4 arcseconds – centered on the EDSGC galaxy coordinates - which seemed appropriate based on our separation analysis. If an EDSGC galaxy had two, or more, possible match-ups, we forced there to be a unique match–up by simply taking the closest LCRS galaxy.

In addition to providing redshift measurements, the LCRS also published (Thuan-Gunn) r–band photometry on all their galaxies which allows us to study the large–scale distribution of galaxy colors ($`b_jr`$) across the entire EDSGC right ascension coverage i.e. the EDSGC overlaps with the $`39^{}`$ and $`42^{}`$ declination strips of the LCRS which span from $`21^{hrs}`$ to $`4^{hrs}`$ in right ascension. Therefore, this provides a significant external check of our photometry since, on average, galaxies should have the same $`b_jr`$ color across the survey, ignoring reddening effects, or real large–scale structure in the universe. We note here that we are not making any claims about the absolute $`b_jr`$ color of galaxies as this would require a detailed analysis of both the EDSGC and LCRS aperture photometry; we are simply examining the large–scale trends in the $`b_jr`$ color as a function of right ascension and original plate number

In Figure 1, we plot the $`b_jr`$ color of all galaxies as a function of right ascension. This plot immediately demonstrates that there is no large–scale systematic error between these two independent photometric systems i.e. the mean galaxy $`b_jr`$ color is a constant over 70 degrees in right ascension for this joint survey. This is more clearly shown in Figure 2a which plots the mean and standard deviation of the $`b_jr`$ color versus right ascension for the EDSGC–LCRS sample. The scatter between these mean points is significantly smaller than the intrinsic scatter seen in the individual galaxy colors (Figure 1) and is fully consistent with the sum of errors on the individual photometric measurements i.e. as discussed above and in CNL92, the rms plate–to–plate scatter for the EDSGC is $`\mathrm{\Delta }m0.08`$ (which does not include the photographic measurement error) while the standard deviation of pairwise galaxy magnitude differences for LCRS galaxies which were measured twice on overlapping “bricks”222 A brick is a $`1.5^{}`$ x $`3^{}`$ region as discussed in Shectman et al. 1996 is $`\sigma _m=0.10`$, for $`16.0<r17.0`$, and $`\sigma _m=0.17`$, for $`17.0<r18.0`$ (see also Figure 3 of Shectman et al. 1996).

To investigate this further, we have plotted in Figure 2b the mean $`b_jr`$ color for the EDSGC–LCRS galaxies as a function of their original EDSGC plate identification and right ascension (there are only LCRS data on 14 of the original 60 EDSGC plates). In this plot, we present the mean EDSGC–LCRS galaxy color for each plate as a function of the mean right ascension of that plate. We have broken the data into the two different LCRS declination slices, i.e. $`39^{}`$ and $`42^{}`$, since the former of these two runs through the center of the EDSGC plates (where the calibration is expected to be best), where the latter runs across the southern edge of the EDSGC (as discussed in Section 2.2.2, we cut the EDSGC at $`42^{}`$ for statistical analyses).

Figure 2b once again demonstrates that there is no large–scale gradient between the two photometric systems. The amplitude of the scatter seen between the mean EDSGC–LCRS galaxy color for $`39^{}`$ declination strip is fully consistent with the rms scatter quoted above and in CNL92.

We note here that the larger scatter seen in Figure 2b for the $`42^{}`$ LCRS declination strip is probably due to photographic plate edge effects. Such edge effects have little consequence on the science of the EDSGC, as outlined in Section 6, since in most cases the data was cut to avoid such edge effects as discussed in Section 2.2.2. The same is true for plates 300, 301 & 344 (regardless of LCRS declination slice) since these three plates are at the corners of the EDSGC where the number of plate overlaps is significantly smaller than for other plates; plate 300 only overlaps with plate 301 which in turn only overlaps with plates 357 & 299. For plate 301, the measured magnitude offset with these overlapping plates is $`\mathrm{\Delta }m_{301357}=0.35`$ and $`\mathrm{\Delta }m_{301299}=0.11`$ i.e. the average magnitude difference for galaxies in common between two plates. This may explain the larger scatter seen for plates 300 & 301 since they are somewhat isolated from the rest of the EDSGC (they are on the southeast corner of the EDSGC). Similarly, Plate 344 is on the southwestern corner of the EDSGC and also suffers from a smaller number of plate overlaps with other plates; it only overlaps with plate 405 ($`\mathrm{\Delta }m_{344405}=0.028`$) and plate 345 ($`\mathrm{\Delta }m_{344345}=0.05`$).

We note that the feature in Figures 1 & 2 near Plate 293 could be due to real large–scale structure. As shown in Guzzo et al. (1992), this area of the EDSGC coincides with both the Sculphor and BS1 superclusters; two of the largest superclusters presently known.

Finally, we have also carried out a similar analysis using the 907 galaxies in common between the ESO Nearby Abell Cluster Survey (ENACS; Katgert et al. 1996) and the EDSGC (ENACS provides a R–band magnitude for all their galaxies). The results are the same as above with the LCRS in that the mean $`b_jR`$ color for EDSGC-ENACS galaxies is a near constant as a function of right ascension.

### 5.2 Star–Galaxy Separation

As discussed in Section 4, the EDSGC has been used for several large galaxy redshift surveys. A by–product of this work is an external check on the star–galaxy separation techniques of the EDSGC since stars are easy to spectroscopically differentiate from galaxies. The best test of this comes from the ESO Slice Project (Vettolani et al. 1997) since they targeted for spectroscopic observations all $`b_j19.4`$ EDSGC galaxies between a right ascension of $`22.5^h`$ and $`1^h\mathrm{\hspace{0.17em}20}^m`$ at a mean declination of $`40.25^{}`$. From this sample, which is 90% complete in observations, only 12% of EDSGC galaxies were stars. This is slightly higher than we observed from our visual checks (Heydon-Dumbleton et al. 1989 quotes $`<10\%`$) of the star–galaxy separations discussed above in Section 2.1.1.

## 6 Discussion

In this section we give a brief review of the science to originate from the EDSGC:

### 6.1 Galaxies

The angular correlation function ($`w(\theta )`$) of the EDSGC and its stability to Galactic extinction and photometric calibration errors are given in CNL92 and Nichol & Collins (1993) respectively. These results confirm the high amplitude of the angular correlation function found by the APM survey (Maddox et al. 1990b) and help demonstrate that the previous results pertaining to the Lick galaxy catalogue (Groth & Peebles 1977) were in error. Higher order correlations have been analysed by Szapudi, Meiksin & Nichol (1996) which are in good agreement with predictions from N-body simulations and suggest that the galaxies are reliable tracers of the underlying mass distribution. A comparison of the large-scale clustering in the APM and EDSGC galaxy surveys was performed by Szapudi & Gaztanaga (1998). On large angular scales the main difference between counts in cells is attributable to the smaller area, and therefore greater edge effects, of the EDSGC compared to the APM. On small scales there is evidence that the EDSGC follow N-body simulations more closely than APM which could be a result of the EDSGC de–blending algorithm. However, none of the differences detected effect the results on large-scale structure or their interpretations as published by the two groups.

The EDSGC has been the parent galaxy catalogue for two extensive redshift surveys: the ESO Slice Project (ESP) and the Durham/UKST Galaxy Redshift Survey. The ESP is an $`85\%`$ complete galaxy redshift survey consisting of $`3300`$ galaxies brighter than $`b_j=19.4`$ in a 23.3 square degree region close to the South Galactic Pole (Vettolani et al. 1997). Most notable are the results on the luminosity function and mean galaxy density (Zucca et al. 1997) which provide clear evidence for a “local” underdensity in the galaxy distribution out to $`140`$ h-1 Mpc. Along with the Las Campanas (Shectman et al. 1996) and Stromlo-APM (Loveday et al. 1996) redshift surveys, the ESP project provides one of the most accurate estimates of the faint end of the galaxy luminosity function. The Durham/UKST Galaxy Redshift Survey consists of a one-in-three sampled survey of $`2500`$ galaxies to $`b17`$ covering the EDSGC area (Ratcliffe et al. 1998). The results of this survey suggest that both the structures on scales 50-100 h-1Mpc and the smaller scale pairwise galaxy velocity dispersion show significant power in excess of the predictions of the standard cold dark matter model. Finally, Knox, Huterer & Nichol (2000) have used this extensive redshift data to compute an angular power spectrum, and its covariance matrix, for the whole EDSGC data and compare these results to cosmological predictions.

### 6.2 Clusters

The work on galaxy clusters from the EDSGC has been particularly productive and includes: publication of the first machine-based cluster catalogue – the EDCC (Lumsden at al 1992); results on the spatial distribution and correlation function of clusters (Guzzo et al. 1992, Nichol et al. 1992); an analysis of the alignments of galaxy clusters (Martin et al. 1995); a study of the cluster galaxy luminosity function from the largest single database ever used to study this problem (Lumsden et al. 1997); a comprehensive redshift survey of rich clusters (Collins et al. 1995). In addition, the EDSGC has been used recently to study the local space density of optical clusters (Bramel, Nichol & Pope 2000) and the relationship between optical and X–ray luminosities of clusters (Miller, Melott & Nichol 2000).

## 7 Acknowledgments

We are grateful to the COSMOS and UK Schmidt units at the Royal Observatory Edinburgh and Anglo–Australian Observatory for their continued support of the EDSGC. We would also like to thank PPARC for their financial support of the EDSGC. We are indebted to Neil Heydon-Dumbleton and Luigi Guzzo for their help and advice over the lifetime of this project and we thank Matthew Colless for making his CCD calibration data available to us. Finally, we thank Marion Schmidt of the NASA/IPAC Extragalactic Database (NED) for his continuing checks of the EDSGC. This work was sponsored in part by NASA grant NAG5-3202 (RCN).