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# Faint galaxy population in clusters: X-ray emission, cD halos and projection effects.

## 1 Introduction

Determining the galaxy luminosity function (hereafter LF) down to faint magnitudes in rich clusters has been the subject of many studies in the last years (e.g. Sandage, Binggeli & Tammann 1985; Driver et al. 1994, De Propris et al. 1995; Lobo et al. 1997; Lumsden et al. 1997; Lopez-Cruz et al. 1997; Valotto et el. 1997; Wilson et al. 1997; Smith et al. 1997; Trentham 1998a; Trentham 1998b; Driver et al. 1998; Garilli et al. 1999). Most of these authors show that galaxy clusters are dominated by a large population of high surface brightness dwarf galaxies, corresponding to a steep faint end slope of the luminosity function, $`\alpha `$ in the range -1.4 to -2.0.

The origin and evolution of this faint galaxy population has important consequences for our current understanding of galaxy formation and evolution in dense environments. For instance, Lopez-Cruz et al (1997) have suggested that the galaxy LF is flat in dynamically evolved clusters characterized by the presence of a dominant cD galaxy, high richness, symmetrical single-peaked X-ray emission, and high gas mass. On the other hand, steep faint-end slopes ($`2.0\alpha 1.4`$) are detected in poorer clusters. It is worth noticing the fact that the galaxy luminosity function of groups selected in redshift space is flat at faint magnitudes (Muriel, Valotto & Lambas, 1998) which shows the lack of a universal trend of the parameter $`\alpha `$ with system richness. More recently, Martinez et al. (2002), have obtained reliable determinations of galaxy LF in groups obtained from the 2dF galaxy redsfhit survey. Their results are consistent with a nearly universal galaxy LF with little dependence on environment which is consistent with these previous findings. Lopez-Cruz et al. (1997) suggest that cD galaxies are formed from the disruption of many faint galaxies in the cluster cores, thus resulting in a globally flat faint end slope. Indeed, dynamical processes operating in relaxed clusters are, in general, destructive. Ram pressure stripping (Gunn & Gott 1972, Abadi, Moore & Bower 1999) and gravitational tides/galaxy harassment (e.g. Moore et al. 1996) both tend to fade galaxies by removing gas or stripping stars. These process are most effective for smaller, less bound galaxies, and would cause a flattening of the faint end slope. However, mergers and galaxy interactions, when the cluster environment then was more like a group environment could have contributed in the opposite direction at early evolutionary stages.

Although large deep redshift surveys of clusters are not presently available, Ferguson & Sandage (1991), and Zabludoff & Mulchaey (2000) have analyzed cluster fields with redshift information and obtained faint end slopes $`\alpha 1.25`$ to $`1.3`$, which are not significantly steeper than field and group measurements in the 2dF galaxy redshift survey, Norberg et al. 2001, Martinez et al. (2002) both consistent with $`\alpha 1.13`$. Most other estimates of galaxy luminosity functions in clusters rely critically on background subtraction and are in general consistent with significantly steeper faint end slopes ($`\alpha 1.5`$). The accuracy of this procedure depends on the statistical assumption that galaxy clusters correspond to density enhancements unbiased with respect to the distribution of foreground or background galaxies. However, significant projection effects are found in Abell clusters (e.g. Lucey 1983, Sutherland 1988, Frenk et al 1990) that can systematically bias the observed correlation function and the mass function of these systems. In fact, van Haarlem et al (1998) claim that one third of Abell clusters are not real physically bound systems but simply projections of galaxies and groups along the line of sight.

Valotto, Moore and Lambas (2001) have analyzed several sources of systematic effects present in observational determinations of the galaxy luminosity function in clusters. They used mock catalogues derived from numerical simulations of a hierarchical universe to identify clusters of galaxies in two dimensions in a similar fashion to Abell 1958 and Abell et al. 1989. Applying standard background subtraction procedures to these data gave rise to artificially steep faint end slopes since many of the clusters do not have significant counterparts in physical space. These projection effects result almost entirely from the large scale structure behind the cluster, a result that was also concluded by Adami et al (2000) from measuring $`100`$ redshifts for faint galaxies thought to lie in the Coma cluster. Color information (eg. b-r) is useful to improve the signal to noise in the process of background decontamination by efficiently removing red background galaxies at $`z0.5`$. However, very unlikely contaminating structures at significantly lower redshifts would be eliminated by the use of colors. See for instance Adami et al. (2000) where a significant number of background galaxies in the field of Coma Clusters are at $`0.02<z<0.3`$.

The X-ray emission of the hot intracluster gas provides a confirmation of the presence of a bound cluster of galaxies. Thus, estimates of the galaxy luminosity function in clusters by means of background decontamination techniques restricted to an X-ray selected sample may provide a useful insight on the issues previously mentioned. In this paper we explore the nature of the faint galaxy population in clusters obtained by background decontamination techniques in X-ray and optically identified clusters of galaxies. By considering a subsample restricted to clusters dominated by a central cD galaxy we can also explore the disruption hypothesis suggested by Lopez Cruz et al (1997).

## 2 Analysis

### 2.1 Cluster samples

The sample of galaxy clusters used in our statistical analysis is taken from Abell et al (1989) cluster catalog and from the X-ray flux-limited sample of Bright X-ray Clusters (De Grandi et al 1999, hereafter BXS), an X-ray selected cluster sample based on the first analysis of the ROSAT All-Sky Survey data (RASS1). This sample is count-rate limited in the ROSAT hard band (0.5-2.0 keV) and its effective flux limits varies between $``$ 3 and 4 $`\times 10^{12}`$ ergs cm-2 s-1.

The region explored is limited to galactic latitude $`b<40\mathrm{°}`$ and declination $`70\mathrm{°}<\delta <10\mathrm{°}`$ and the area covered by the RASS1 Bright Sample. This survey area is restricted to regions with high exposure time ($`>`$150s), excluding the sky areas of the Galactic plane and the Magellanic clouds to avoid incompleteness in the cluster sample. Due to the lack of homogeneity of the sky coverage of the ROSAT All-Sky Survey, we have checked the positions of those Abell clusters with no X-ray counterpart to eliminate from the statistics objects in the poorly sampled regions (see Figure 1).

In the area considered there are 34 Abell clusters and 15 X-ray clusters with redshift $`z<0.06`$. Eight of these Abell clusters are identified with X-ray emission in this sample. Table 1 and table 2 list angular positions (J2000.0), mean redshifts, richness number counts and Bautz-Morgan types for the different samples analyzed here taken from Abell, Crowin & Olowin 1989. A low redshift cutoff is required in order to reach faint absolutes magnitudes which unambiguously determine the $`\alpha `$ parameter.

### 2.2 LF Determination

The Edinburgh-Durham Southern Galaxy Catalog, hereafter COSMOS Survey (Heydon-Dumbleton et al 1989), was used for the statistical assignment of galaxies to the clusters. This survey provides angular positions and photographic magnitudes in the $`b_j`$ band for over two million galaxies. We have restricted to the region $`\delta <10\mathrm{°}`$ given the lower quality in the photographic material in the northern hemisphere. We use a limiting apparent magnitude, $`b_j=20.0`$ (Valotto et al 1997), for our analysis of the COSMOS Survey which minimizes errors due to misclassification of stars, galaxies plate variations, etc. Incompleteness effects arise mainly due to star-galaxy misclassification. In the COSMOS survey the latter is expected to be lesser than 10% at m=20.5,and completeness to be greater than 99.5 % at $`b_j`$=19.5 (see Szapudi & Gaztañaga, 1998 for a comparison between COSMOS and APM survey statistical properties).

The counts of galaxies for each cluster are binned in equal number intervals. We subtract the corresponding mean background correction to each magnitude bin to compute the contribution from each cluster to the LF. We compute the number of galaxies brighter than a limiting absolute magnitude $`M_{lim}`$ within a projected radial distance $`r`$ from the cluster centers. The limiting absolute magnitude used is $`M_{lim}=16.5`$. We have applied a $`K`$correction term of the form $`K=3z`$ (Efstathiou, Ellis & Peterson 1988). The projected radius $`r`$ is fixed at $`1.0`$ $`h^1`$ $`Mpc`$. We assume the Hubble constant is $`H_0=100h`$ km $`s^1`$ Mpc-1, similar to that adopted in other studies. Since cluster redshifts are very small (z¡0.06) we simply use the local euclidean approximation.

We define a mean local background around each cluster in order to perform a statistical background subtraction. This mean local background is defined as the number density of galaxies in the same range of apparent magnitudes in a ring at projected radii $`R_1<r<R_2`$. We have used $`R_1=6`$ Mpc h-1 and $`R_2=8`$ Mpc h-1.

According to Valotto et al. (1997) the stability of the results does not depend crucially on the projected clusters radii nor on the adopted radius for the background correction provided that the decontamination ring is well beyond the average projected radius of the clusters and small enough in order to take into account local variations of the projected galaxy density due to patchy galactic obscuration, large scale gradients in the galaxy catalog, etc.

For all samples we compute error bars in the galaxy LF through bootstrap resampling of the clusters to provide an estimate of the variations from cluster to cluster.

In order to provided suitable fits for the galaxy luminosity functions, we have adopted a Schechter function model $`\varphi (L)dL=C\times (L/L^{})^\alpha e^{L/L^{}}d(L/L^{})`$, where $`C`$ is a constant (Schechter 1977). We have applied a maximum likelihood estimator using the $`\chi ^2`$-estimator procedure, which minimize the difference

$$\chi ^2=\underset{i=1}{\overset{N}{}}\left[\frac{\varphi _i\varphi (L_i;C,\alpha ,L^{})}{\sigma _i}\right],$$

where $`\varphi _i`$ is the relative frequency of galaxies corresponding to the $`i`$th bin and $`\sigma _i`$ is its associated uncertainty. All galaxy luminosity functions where arbitrarily normalized in order to make a proper comparison of their shapes.

## 3 Results

In this section we discuss the results obtained from the analysis of our cluster samples defined above. In Figure 2 we show the galaxy LF for the sample of bright X-ray clusters. For comparison we show the LF for the sample of Abell clusters in the same area of the sky and for the same range of redshifts. The solid lines correspond to Schechter function fits with parameters $`\alpha =0.9\pm 0.1`$, $`M^{}=19.0\pm 0.2`$ and $`\alpha =1.50\pm 0.1`$, $`M^{}=20.3\pm 0.2`$ for the X-ray and Abell samples respectively. The X-ray defined cluster sample has a significantly flatter faint end slope than the sample of Abell clusters.

We have also computed the galaxy LF for two subsamples of Abell clusters: those confirmed by the X-ray intracluster emission, and those with no X-ray detection. The results for these two samples are shown in Figure 3. Again we find a clear difference in the LF of clusters with and without X-ray emission. Abell clusters with no detected X-ray emission show a very steep galaxy LF faint end which contrasts with the flat behavior of the galaxy LF in X-ray confirmed clusters. The corresponding Schechter fits are $`\alpha =1.0\pm 0.1`$, $`M^{}=18.9\pm 0.2`$ and $`\alpha =1.6\pm 0.1`$, $`M^{}=20.6\pm 0.2`$ for the Abell clusters with and without X-ray detection respectively

A main point in the analysis of Lopez-Cruz et al (1997) is the suggestion that cD halos could be formed by accretion and disruption of galaxies resulting in a flattening of the faint end slope of the LF. Lopez-Cruz et al (1997) have suggested a scenario where the flat faint end of the galaxy LF in relaxed clusters results from the disruption of dwarf galaxies during the early stages of cluster evolution which also may explain the halos of central cD galaxies and a substantial fraction of the intracluster medium. We have tested this hypothesis by computing the galaxy LF for a subsample of clusters with Bautz-Morgan (BM) types I and I-II characterized by the presence of a dominant cD galaxy (this restricts our analysis to Abell clusters for which BM types are available). The first subsample corresponds to clusters selected in X-rays and the second subsample to clusters with no detection of X-ray emission. The results shown in Figure 4 suggests that the BM type of the clusters does not determine the faint end galaxy LF. Clusters with no detected X-ray emission have steep galaxy LF , on the contrary, clusters with detected X-ray emission show flat galaxy LF at the faint end.

The corresponding Schechter fits are $`\alpha =1.0\pm 0.1`$, $`M^{}=19.1\pm 0.1`$ and $`\alpha =1.7\pm 0.2`$, $`M^{}=20.2\pm 0.2`$ for the X-ray and non x-ray subsamples respectively. This test indicate that the detection of a faint population of faint galaxies is not correlated with dominant central galaxies but with the X-ray confirmation.

In Lopez-Cruz et al. 1997 scenario, it would also be expected that the slope of the faint end LF should correlate with the X-ray luminosity, i.e. the most luminous X-ray clusters should have the flattest galaxy LF faint end slopes. We explore this possibility by dividing our X-ray cluster sample into equal numbers of clusters corresponding to high and low X-ray luminosity ($`L_x>1.0\times 10^{44}`$ ergs cm-1 s-1 and $`L_x<1.0\times 10^{44}`$ ergs cm-1 s-1) which correspond to mean luminosities of 2.44 and $`0.83\times 10^{44}`$ ergs cm-1 s-1 respectively.

The resulting LF’s are shown in Figure 5 and we find no differences between the two subsamples ($`\alpha =1.1\pm 0.3`$, $`M^{}=18.6\pm 0.2`$ and $`\alpha =1.1\pm 0.3`$, $`M^{}=18.8\pm 0.2`$ for low and high X-ray luminosity sample respectively), although the numbers of clusters in each sample is small. This result indicates that it is the detection of the intracluster medium through the X-ray emission and not its luminosity that correlates with the faint end slopes, giving support to the hypothesis of strong projection contamination in optically identified cluster samples.

We have analyzed samples of clusters which no dominant central galaxies, i.e. BM types II, II-III and III. We confirm here that, again, X-ray detectability and not the presence or absence of dominant central galaxies correlates with the $`\alpha `$ parameter obtained from background decontamination.

In order to test far a possible dependence of our results on cluster radii, we have analyzed all samples within two different limiting radii, $`R=0.5h^1`$ Mpc and $`R=1.0h^1`$ Mpc. We find similar results for these two samples which indicates a lack of strong radial dependence (see however de Propis et al. 1995).

Table 3 summarizes all of the parameters for the Schechter function fits to the various cluster subsamples. (We find no difference in our measurements of the faint end slope when we constrain the value of $`M^{}`$ to be the same value for each data set.)

We have also explored the ratio of dwarf to giant galaxies (D/G, D: $`18.5<B_j<16.5`$, G: $`24<B_j<18.5`$) in order to test the stability of our results when Schechter functions give poor fits to the actual LF. We have computed the D/G ratios for all samples analyzed and we show the results in table 3. As it can be seen by inspection to this table D/G and $`\alpha `$ are strongly correlated, all clusters with $`\alpha >1.2`$ have D/G $`<4`$ while samples with raising faint end slopes, $`\alpha <1.4`$, have D/G $`>5`$. Thus, D/G ratios provide confidence on our faint end slope estimates.

## 4 Discussion and Conclusions

We have analyzed the galaxy LF obtained by background decontamination techniques in samples of nearby clusters taken from Abell et al. 1989 and the Bright X-ray Cluster Catalogues (De Grandi et al. 1999). We find that X-ray selected clusters show an apparently flat luminosity function consistent with that derived for the field and groups($`\alpha 1`$). By contrast, clusters of galaxies identified from the projected galaxy distribution that do not have an X-ray counterpart show a galaxy luminosity function with a very significant steeper faint end ($`\alpha 1.5`$).

We find that for the subsample of clusters with dominant central galaxies (Bautz-Morgan type I and I-II) the shape of the faint end galaxy LF depends on the detection of the X-ray emission of the intracluster gas. In fact, we derive a steep galaxy LF for the subsample of clusters with central dominant galaxies with no detected X-ray intracluster emission. This fact argues against the hypothesis that the disruption of faint galaxies would provide the material out of which cD halos form causing a flattening of the faint end slope. A note of caution should be set here since we have used Bautz-Morgan classes as a suitable division between cD and non-cD clusters. Although some BM type I and I-II clusters may not contain bonafide cD galaxies, these clusters are strongly dominated by a central galaxy, so it is on the global, statistical sense that our analysis provide a test of Lopez-Cruz et al. hypothesis.

Our results could be influenced by the possibility that many X-ray undetected clusters could be bound systems less dynamically evolved and therefore with a large fraction of emission line galaxies which have a steeper alpha than non-emission line galaxies (Madgwick et al. 2002). Nevertheless, Martinez et al. 2002 have shown that even low mass groups ($`M_{virial}10^{13}10^{14}M_{}`$) in the 2dF galaxy redshift survey are dominated by absorption line type galaxies suggesting that this is not a very serious possibility.

More likely, our results provide support to the presence of biases on the cluster galaxy LF derived by background decontamination procedures due to projection effects, as suggested by Valotto, Moore and Lambas (2001). Clusters identified from the projected galaxy distribution are biased by many spurious clumps with no physically bound system along the line of sight. The resulting luminosity functions from background decontamination procedures show steep faint end slopes and can be erroneously interpreted as the clusters being dominated by a population of dwarf galaxies. Furthermore, the fact that no significant correlation between X-ray luminosity and the galaxy LF faint end slope is found argues against processes associated to the gaseous environment causing the differences in the galaxy LF faint end slope.

## 5 Acknowledgments

We thank the anonymous Referee for very helpful suggestions which greatly improved the previous version of this paper. This research was supported by grants from Agencia Córdoba Ciencia, Secretaría de Ciencia y Técnica de la Universidad Nacional de Córdoba, Fundación Antorchas, and Agencia Nacional de Promoción Científica, Argentina. CV is supported by the National Science Foundation through grant #GF-1003-00 from the Association of Universities for Research in Astronomy, Inc., under NSF cooperative agreement AST-9613625.


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# References

Some deformations of $`U\mathbf{[}sl\mathbf{(}\mathrm{𝟐}\mathbf{)}\mathbf{]}`$
and their representations

Nguyen Anh Ky
Institute of Physics

P.O. Box 429, Bo Ho, Hanoi 10 000, Vietnam

## Abstract

Some one- and two-parametric deformations of U\[sl(2)\] and their representations are considered. Interestingly, a newly introduced two-parametric deformation admits a class of infinite - dimensional representations which have no classical (non-deformed) and one-parametric deformation analogues, even at generic deformation parameters.

PACS: 02.20Uw, 03.65.Fd, MSC: 17B37, 20G05.

1. Introduction

For over two decades, quantum groups  \-  have been a subject of great interest in physics and mathematics. A number of mathematical structures and physical applications of quantum groups have been obtained and investigated in details  \- . Depending on points of view, quantum groups can be approached to in several ways. One of the approaches to quantum groups are the so-called Drinfel’d-Jimbo deformation of universal enveloping algebras . It is shown that the quantum groups of this kind (called also quantum algebras) are non-commutative and non-cocommutative Hopf algebras . By construction, such a quantum group depends on one or more parameters which are, in general, complex. One-parametric deformations have been well investigated and understood in various aspects, while multi-parametric deformations are less understood, in spite of some research progress made lately (see  \-  and references therein). In this report, we consider some one- and two-parametric deformations of the universal enveloping algebra $`U[sl(2)]`$ and their representations.

The quantum group $`U_q[sl(2)]`$ as an one-parametric deformation of the universal enveloping algebra $`U[sl(2)]`$ is one of the best investigated quantum groups  \- . What about two-parametric deformations of $`U[sl(2)]`$, they have been considered in several versions and in different aspects (see, for example,  \-  and references therein) though some of them are, in fact, equivalent to one-parametric deformations (upto some rescales). In this report we consider only two of them, denoted here by $`U_{pq}^{(1)}[sl(2)]`$ and $`U_{pq}^{(2)}[sl(2)]`$ (a common notation is $`U_{pq}[sl(2)]`$). The first quantum group $`U_{pq}^{(1)}[sl(2)]`$ was already given before as a subgroup of a quantum supergroup , while the second one, $`U_{pq}^{(2)}[sl(2)]`$, is being introduced now. It turns out that this new quantum group $`U_{pq}^{(2)}[sl(2)]`$ admits a class of infinite - dimensional representations which have no analogue in either the case of the non-deformed $`sl(2)`$ or the cases of previously introduced one- and two-parametric deformations of $`U[sl(2)]`$. For consistency, we first consider the non-deformed $`sl(2)`$, the one-parametric deformation $`U_q[sl(2)]`$ and the two-parametric deformations $`U_{pq}^{(1)}[sl(2)]`$ in the next three sections, Sect. 2, Sect. 3 and Sect. 4, respectively. Then the two-parametric deformations $`U_{pq}^{(2)}[sl(2)]`$ is introduced and considered in Sect. 5. Some discussions and conclusion are made in the last section, Sect. 6. Let us start now with $`sl(2)`$.
2. $`sl\mathbf{(}\mathrm{𝟐}\mathbf{)}`$ and representations

As is well known, $`sl(2)`$ can be generated by three generators, say $`E_+`$, $`E_{}`$ and $`H`$, satisfying the commutation relations

$$[H,E_\pm ]=\pm E_\pm ,[E_+,E_{}]=2H.$$
$`(1)`$
Demanding $`(H)^{}=H`$ and $`(E_\pm )^{}=E_{}`$, a representtaion induced from a (normalised) highest weight state $`|j,j`$,

$$H|j,j=j|j,j,E_+|j,j=0,$$
$`(2)`$
has the matrix elements

$$H|j,m=m|j,m,$$

$$E_\pm |j,m=\sqrt{(jm)(j\pm m+1)}|j,m\pm 1,$$
$`(3)`$
where $`|j,m`$, $`mj`$, is one of the orthonormalised states which can be obtained by acting an appropriate monomial of $`E_{}`$ on the highest weight state $`|j,j`$,

$$|j,m=A_n(E_{})^n|j,j,m=jn,$$
$`(4)`$
with $`A_n`$ a normalised coefficient, which for a non-negative (half) integral highest weight $`j`$ has the form

$$A_n=\sqrt{\frac{(2j)!n!}{(2jn)!}}.$$
$`(5)`$
In this case, the representations constructed are simultaneously highest weight and lowest weight, that is,

$$E_+|j,j=0,E_{}|j,j=0,$$
$`(6)`$
so, they are finite-dimensional (and also unitary and irreducible) of dimension $`2j+1`$ (with $`m`$ taking by steps of 1 all values in the range $`jmj`$). The situation is similar in the case of the one-parametric quantum group $`U_q[sl(2)]`$ at a generic deformation parameter $`q`$ (i.e., at $`q`$ not being a root of unity).
3. One-parametric deformation $`U_q\mathbf{[}sl\mathbf{(}\mathrm{𝟐}\mathbf{)}\mathbf{]}`$

As mentioned above, $`U_q[sl(2)]`$ is one of the best investigated quantum groups. It can be defined through three generators $`E_+`$, $`E_{}`$ and $`H`$ subject to the deformed defining relations

$$[H,E_\pm ]=\pm E_\pm ,[E_+,E_{}]=[2H]_q,$$
$`(7)`$
where

$$[X]_q=\frac{q^Xq^X}{qq^1},$$
$`(8)`$
is the so-called one-parametric deformation (or $`q`$-deformation, for short) of an operator or a number $`X`$, with $`q`$ being a, complex in general, parameter. At a generic $`q`$, the representation structure of $`U_q[sl(2)]`$ is similar to that of $`sl(2)`$, more precisely, a representation of $`U_q[sl(2)]`$ induced in the same way (as done for $`sl(2)`$) from a highest weight state $`|j,j`$ defined as in (2) has the matrix elements

$$H|j,m=m|j,m,$$

$$E^\pm |j,m=\sqrt{[jm]_q[j\pm m+1]_q}|j,m\pm 1.$$
$`(9)`$
These representations are again of finite dimension $`2j+1`$ (and irreducible as $`q`$ is generic) for non-negative (half) integral highest weights $`j`$, since Eqs. (6) are again satisfied (i.e., the representations are again highest weight and lowest weight simultaneously).
4. A two-parametric deformation $`U_{pq}^{\mathbf{(}\mathrm{𝟏}\mathbf{)}}\mathbf{[}sl\mathbf{(}\mathrm{𝟐}\mathbf{)}\mathbf{]}`$

The quantum group $`U_{pq}^{(1)}[sl(2)]`$ considered here is only one of the two-parametric deformations of $`U[sl(2)]`$ introduced in the literature. Appeared in  as a subgroup of a quantum supergroup $`U_{pq}[gl(2/1)]`$, this quantum group can be generated by three generators $`E_+`$, $`E_{}`$ and $`H`$ satisfying somewhat more twisted defining relations

$$[H,E_\pm ]=\pm E_\pm ,[E_+,E_{}]=\left(\frac{p}{q}\right)^{JH}[2H]_{pq},$$
$`(10)`$
where $`J`$ is the so-called the ”maximal spin” (or the hight weight) operator and

$$[X]_{pq}=\frac{q^Xp^X}{qp^1},$$
$`(11)`$
is a notation for a two-parametric deformation (or $`pq`$-deformation) of an operator or a number $`X`$, with $`p`$ and $`q`$ being deformation parameters which are in general complex. Constructed in the same way for generic $`p`$ and $`q`$, the (highest weight) representations of $`U_{pq}^{(1)}[sl(2)]`$ are similar to those of $`U_q[sl(2)]`$ and $`sl(2)`$,

$$H|j,m=m|j,m,$$

$$E^\pm |j,m=\sqrt{[jm]_{pq}[j\pm m+1]_{pq}}|j,m\pm 1.$$
$`(12)`$
They are again finite - dimensional for non-negative (half) integral $`j`$. Although the quantum supergroup $`U_{pq}[gl(2/1)]`$ is not equivalent to an one-parameter deformation of $`U[gl(2/1)]`$, its subgroup $`U_{pq}^{(1)}[sl(2)]`$ can be shown to be equivalent to an one-parametric deformation of $`U[sl(2)]`$. The situation is, however, different in the next case.
5. An alternative two-parametric deformation $`U_{pq}^{\mathbf{(}\mathrm{𝟐}\mathbf{)}}\mathbf{[}sl\mathbf{(}\mathrm{𝟐}\mathbf{)}\mathbf{]}`$

Now we introduce an alternative two-parametric quantum group $`U_{pq}^{(2)}[sl(2)]`$ generated also by three generators $`E^+`$, $`E^{}`$ and $`H`$ but the latter now satisfy defining relations simpler than those of $`U_{pq}^{(1)}[sl(2)]`$,

$$[H,E^\pm ]=\pm E^\pm ,[E^+,E^{}]=[H]_{pq}.$$
$`(13)`$
Following the way of constructing highest weight representations in the previously considered cases, we find representations of $`U_{pq}^{(2)}[sl(2)]`$ corresponding to (3), (9) and (12),

$$H|j,m=m|j,m,$$

$$E^+|j,m=\left(\frac{q^{j+m+1}[jm]_qp^{jm1}[jm]_p}{qp^1}\right)^{1/2}|j,m+1,$$

$$E^{}|j,m=\left(\frac{q^{j+m}[jm+1]_qp^{jm}[jm+1]_p}{qp^1}\right)^{1/2}|j,m1.$$
$`(14)`$
In comparison with the case of $`U_{pq}^{(1)}[sl(2)]`$, for the sake of simplicity of the difining relations, the matrix elements in this case become a bit more complicated. Moreover, even at a non-negative (half) integral highest weights $`j`$, we observe that representations of the form (14) are, in general, infinite - dimensional, unlike those of $`sl(2)`$, $`U_q[sl(2)]`$ and $`U_{pq}^{(1)}[sl(2)]`$ in (3), (9) and (12), respectively. These representaions of $`U_{pq}^{(2)}[sl(2)]`$ are still highest weight by construction but they are no longer lowest weight for arbitrary $`p`$ and $`q`$. It is a new class of infinite - dimensional representations of $`U_{pq}[sl(2)]`$ not found before in the cases of $`sl(2)`$ and its previously considered deformations. Note that $`U_{pq}^{(2)}[sl(2)]`$ is by no means equivalent to the one-parametric $`U_q[sl(2)]`$ unless at $`p=q`$ and at, maybe, other special choices of $`p`$ and $`q`$.
6. Conclusion

We have introduced a new quantum group $`U_{pq}^{(2)}[sl(2)]`$ which is a two-parametric deformation of $`U[sl(2)]`$. Interestingly, it is showed that this quantum group admits a class of infinite - dimensional representations which have no analogues in the prviously considered cases of the non-deformed $`sl(2)`$, the one-parametric deformation $`U_q[sl(2)]`$ and other two-parametric deformations of $`U[sl(2)]`$. It is a new phenomenon of $`U_{pq}^{(2)}[sl(2)]`$.
Proposition 1: Highest weight representations of the two-parametric quantum algebra $`U_{pq}^{(2)}[sl(2)]`$ defined in (10) and (11) are in general infinite - dimensional, even for non-negative (half) integral highest weights.

These representations are still unitary and, in general, irreducible. They may become reducible under certain additional conditions such as one or both of the deformation parameters to be roots of unity or at some other special choices if allowed. However, in these cases, it is possible to extract finite - dimensional irreducible representations from the infinite - dimensional reducible ones.
Proposition 2: The representations (14) are reducible and contain finite-dimensional subrepresentations iff the equation

$$f(x)q^{2jx}[x+1]_qp^{2j+x}[x+1]_p=0$$
$`(15)`$
has positive intergral solutions.

Other classes of infinite - dimensional representations of $`U_{pq}[sl(2)]`$ may be found by using the method of .
Acknowledgement: I would like to thank Randjbar - Daemi for kind hospitality at the Abdus Salam International Centre for Theoretical Physics, Trieste, Italy, where some years ago a stage of this investigation was dealt with. Inspiring discussions with Vo Thanh Cuong and Nguyen thi Hong Van are also acknowledged. This work was partially supported by the Vietnam National Research Program for Natural Sciences under Grant 411101.


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# Vibrational Spectra of the Azabenzenes Revisited: Anharmonic Force Fields

## I Introduction

For atomization energies and geometries, density functional theory (DFT) constitutes a cost-effective alternative to wavefunction-based ab initio methods, being capable of accuracies on the order of a few kcal/mol and a few picometer, respectively, if basis sets of polarized triple zeta quality are employedHCTH407 ; BMH .

As a result of this astonishing success, especially considering the modest computational cost of DFT methods, a variety of new applications are now being exploredColwell ; Jamorski ; Bauernschmitt ; Carole ; AmosDP , including, very recently, the calculation of molecular anharmonic potential energy surfaces thiel . Anharmonic potential energy surfaces (see Refs.Clabo88 ; Allen90  for initial pioneering studies at the SCF and CISD level) allow for the prediction of molecular vibration-rotation spectra that can be compared directly to experiment, obviating the need to make estimations or approximations for the effect of anharmonicity. CCSD(T)/$`spdf`$ anharmonic force fields can achieve accuracies on the order of 10 cm-1 or better for fundamentals (e.g. c2h4  and references therein), and even greater accuracy is achievable if still larger basis sets and corrections for inner-shell correlation are consideredc2h2 ; diatomichydrides .
DFT anharmonic force fields for small molecules have recently been the subject of two validation studiesNeugebauer ; AnharmVal . Our own validation studyAnharmVal  suggested that, for fundamental frequencies, an RMS accuracy of about 18 cm-1 can be attained when using the B97-1 functional with sufficiently large basis sets. The question arises as to how capable DFT is to treat medium-sized organic molecules in this fashion. Particularly relevant here is the study the study of Miani et al.anharmhandy  on the fundamental frequencies of benzene, which employed the B3LYPBec93 ; Lee88  functional with the TZ2P (triple-zeta plus double polarization) basis set. This paper, as well as a more recent study of furan, pyrrole and thiopheneRudolf , in fact yielded even more accurate results on these medium-sized organic systems than suggested by the small-molecule validation studies cited above.
The azabenzenes are obtained by systematically replacing CH moieties in benzene by nitrogen atoms. Numerous experimental spectra of these compounds are available in the literature, ranging from mono-azabenzene (pyridine) to 1,2,4,5-tetraazabenzene (s-tetrazine). Pentazine is quite elusivePentazide ; the equally elusive N6 (hexazine or hexaazabenzene) molecule has been the subject of extensive theoretical studiesSaxe83 ; RJB2002 : at the CCSD(T)/cc-pVTZ level, the hexazine (hexaazabenzene) structure undergoes distortion from the idealized $`D_{6h}`$ ring to a $`D_2`$ geometry, which is a local minimum situated some 23 kcal/mol above the $`C_{2h}`$ diazide global minimumRJB2002 . Straka recently made the interesting suggestion that cyclic N6 may form very stable M($`\eta ^6`$-N6) complexes with M=Ti, Zr, Hf, ThStraka2002 .

In practice, nine molecules are relevant to the present study: the parent benzene molecule, pyridine, pyridazine, pyrimidine, pyrazine, 1,2,3-triazine, 1,2,4-triazine, 1,2,5-triazine (sym-triazine) and 1,2,4,5-tetrazine (s-tetrazine). All molecules are displayed in figure 1.
Azabenzene skeletons serve as building blocks in nature, e.g., pyridine in pyridixol (vitamin B6), pyridazine and pyrimidine in pteridine, itself found in folic acid (vitamin vitamin B10) and riboflavin (vitamin B2). Moreover the four DNA bases are derivates of pyrimidine (C, T) and of purine (A, G) — itself a pyrimidine-imidazole fused ring system. For these reasons, azabenzene-like compounds figure in drug design, e.g. the reverse transcriptase inhibitors AZT (contains pyrimidine) or nevirapine (contains pyridine). Derivatives of pyridazine have been found to have potential therapeutic or plant growth inhibitory effects.
Quite different applications include melamine-based plastics (melamine is a derivative of s-triazine) and the potential use of s-tetrazine in molecular data storage applications (one of the relaxation mechanisms of the $`S_1`$ state leads to 2 HCN+N2.Sch87 ; Luthi ; tetr1 ; tetr2 ; tetr3 ).
Innes, Ross and Moomaw (IRM throughout this paper) published a compilation and critical review of experimental vibration spectroscopic data current to 1988Moomaw . One of us (with C. Van Alsenoy) carried out a harmonic-only B3LYP/cc-pVTZ study of the vibrational frequencies and geometries.first  The limitations of this approach are obvious.

In the present contribution, we will consider DFT anharmonic force fields and anharmonic vibrational spectra — which are directly comparable to experiment — for the azabenzenes, and demonstrate their power as a spectroscopic assignment tool for medium-sized organic molecules.

## II Computational Details

In our validation studyAnharmVal , we considered a wide variety of exchange-correlation functionals, as well as convergence in terms of the basis set and the integration grids (both Kohn-Sham, KS, and Coupled Perturbed Kohn-Sham).

Especially for organic molecules, we found the best performance to be delivered by the B97-1 functional, which is Handy’s reparametrizationHCTH93  of Becke’s 1997 hybrid functionalB97 . Satisfactory basis set convergence was generally found to be achieved with the TZ2P basis setTZ2P . This is therefore the functional/basis set combination employed for the present study.

We foundAnharmVal  results for anharmonic force field calculations to be exceedingly dependent on the KS integration grid, much less so on the CPKS grid. For the present study, we ended up using a (200,974) grid, that is, the direct product of a 200-point Euler-MacLaurin radial grid with a 974-point Lebedev angular grid. For the CPKS steps, we employed a (75,194) grid, which considerably reduced the overall computational cost. Neither grid was pruned.

The quartic force fields were calculated by numerical central differences (in rectilinear normal coordinates) of analytical second derivatives, using a stand-alone driver program adapted from the CADPAC electronic structure program systemCadpac . The actual DFT second derivative calculations were done using the Gaussian 98 Rev. A11 program packageg98 .

The step size in a numerical derivatives calculation always represents a compromise between discretization error and roundoff error. Based on experience, we determined the step size as a functions of both the absolute value of the harmonic frequency associated with the normal coordinate involved, and the associated reduced mass ($`\sqrt{\frac{1}{_{j,k}(\frac{l_{MW,jk}(i)}{\sqrt{m_j}(i)})^2}}`$):

$`q_{step}(i)=4\times \sqrt{{\displaystyle \frac{1}{_{j,k}(\frac{l_{MW,jk}(i)}{\sqrt{m_j}(i)})^2}}}\times \sqrt{{\displaystyle \frac{1000}{\omega (i)}}}`$ (1)
In order to reduce roundoff error as much as possible, the KS and CPKS equations were basically converged to machine precision.

To calculate this factor, both the reduced mass of the mode $`m_j`$ and the eigenvalues of the normalisation matrix $`l_{MW,jk}`$ are needed. The last part of equation 1, depending on the harmonic frequencies $`\omega `$, additionally ensures that each displaced geometry has approximately the same energy difference to the minimum geometry.
In this manner, we obtain a complete cubic force field, as well as all the diagonal and semidiagonal quartic force constants. These are sufficient for second-order rovibrational perturbation theory analysesrovib1 ; rovib2 ; rovib3 ; rovib4 ; rovib5 , which were carried out using the SPECTROSpectro  and POLYADPolyad  programs developed in the Cambridge group and at Weizmann, respectively.

## III Results and Discussion

### III.1 Benzene

The parent molecule of our series, benzene (Figure 1a), has been the subject of a few previous anharmonic force field studies, two at the SCF/DZP levelMHAJ ; HW , and a very recent one at the B3LYP/TZ2P levelanharmhandy . An extensive experimental literature exists on the subject (see Refs.GOT ; anharmhandy  for reviews): high resolution data are available for many of the fundamentals, and all the assignments can be regarded as conclusive. (An analysis of the B3LYP/cc-pVTZ normal modes of benzene and the azabenzenes in terms of Pulay’s redundant internal coordinates can be found in Table 17 of Ref.first .)

Experimentally obtaining harmonic frequencies for a molecule this large, even with such high symmetry, is a nearly impossible task. In Table 1 we compare computed harmonic frequencies with selected prior calculations (in particular CCSD(T)/$`spdf`$ databenzccsdt ), as well as several sets of experimentally derived data. The first such set are the ‘$`\omega _{av}`$’ estimates of Handy, Murray and Amos (HMA)HMA , themselves obtained as averages of an empirical estimate by Goodman, Ozkabak, and Thakur (GOT)GOT  and their own combination of experimental fundamentals with the SCF/DZP computed anharmonicities of Maslen et al.MHAJ . The second set are derived from the experimental fundamentals and a new SCF/DZP anharmonic analysis by Handy and Willetts (HW)HW . The third set is derived from the experimental fundamentals and the B3LYP/TZ2P anharmonicitiesanharmhandy , and is expected to be the most reliable.
Both sets of DFT numbers compare about equally well with the CCSD(T) data. The C-H stretching frequencies are underestimated by about 20 cm-1, while all other frequencies are being reproduced very accurately. (As an aside, we note that the C–H underestimation problem also occursbenzeneMP2  at the Møller-Plesset perturbation theory (MP2) level.) Although the C–H stretches are reproduced marginally worse by the B97-1 functional (3 cm-1) compared to the reference CCSD(T)/$`spdf`$ values, the overall performance is improved: the mean absolute error decreases from 9.3 (B3LYP) to 6.5 (B97-1) cm-1, and the RMS deviation from 10.6 (B3LYP) to 9.6 (B97-1). The smaller decrease for the RMS error (compared to the mean absolute error) can be attributed to the greater proportional weight given to larger errors. When excluding the C-H stretching frequencies, the RMS errors decrease to 8.4 (B3LYP) and 4.3 cm-1 (B97-1). Considering the computational cost of density functional theory, the B3LYP results are already of spectacular compared to the reference ab initio data. The B97-1 functional, however, reduces the RMS error of the non C-H stretching frequencies by an additional 50%.
Both functionals yield excellent agreement with experiment for the fundamental frequencies (Table 2). The experimental data were taken from the earlier compilation of GOTGOT  and from more recent gas-phase measurementsanharmhandy . The two sets of experimental data agree very well with each other, except for $`\nu _{16}`$ and $`\nu _{12}`$ which are involved in strong Fermi resonances. To obtain the B97-1/TZ2P fundamentals, we had to take the following Fermi resonances into consideration: $`\nu _3+\nu _{16}`$ and $`\nu _{15}`$ (with the deperturbed frequency $`\nu _{15}`$ at 3018 cm-1 and the combination at 2947 $`cm^1`$), $`\nu _{13}+\nu _{16}`$ and $`\nu _{12}`$ (unperturbed $`\nu _{20}`$ at 3040 and the combination band at 3082 $`cm^1`$), $`\nu _{16}+\nu _{13}`$ and $`\nu _5`$ (with the unperturbed frequencies at 3064 and 3020 $`cm^1`$), and $`\nu _2+\nu _{18}`$ and $`\nu _{16}`$ (with $`\nu _{16}`$ (unperturbed) at 1600, $`\nu _2+\nu _{18}`$ at 1603 $`cm^1`$).
Interestingly, because of the small differences in the harmonic frequencies between the B3LYP/TZ2P and the B97-1/TZ2P calculations and the different force field, now new Fermi resonances are predicted. Furthermore, the fundamentals affected by these resonances are the ones which differ the most when using the B3LYP or B97-1 functional. Because of the Fermi resonances, the difference between different functionals and methods becomes more important than on the harmonic level of approximation. The results of both functionals compared to experiment are, however, very similar, with mean absolute errors (compared to the latest experimental results of Miani et al.anharmhandy ) of 9.4 (B3LYP) and 8.3 (B97-1) cm-1 and RMS errors of 17.0 and 13.7 cm-1, respectively. Again, all frequencies are very well described with the exception of the C-H stretches, which are underestimated by 16–30 cm-1 (discounting $`\nu _5`$ which is severely perturbed by resonances). Without the C-H stretches, the mean absolute errors are reduced to 3.7 (B3LYP) and 3.9 (B97-1) cm-1 and the RMS errors to 4.8 (B3LYP) and 4.5 cm-1 (B97-1). Hence, while clearly better for harmonic frequencies, the B97-1 functional is only slightly better for predicting the fundamental frequencies of benzene. Nevertheless, the accuracy obtained by density functional theory, which yields RMS errors of less than 5 cm-1 for non C-H stretching frequencies, is very good.
In the third column, we added the B97-1/TZ2P anharmonic corrections to the CCSD(T)/ANO4321 harmonic frequencies of Ref.benzccsdt , in order to see how such a ‘hybrid’ ab initio-DFT approach would perform. The principal improvement seen is for the C–H stretches, which are thus all bought into the range of the experimental values, except for $`\nu _5`$, which is in resonance with $`\nu _{16}+\nu _{13}`$ as discussed above. When discounting C–H stretching frequencies, the improvement compared to a pure B97-1/TZ2P calculation is quite modest, to 3.1 cm-1 for the mean absolute error and to 4.1 cm-1 for the RMS error. The corresponding error statistics including C–H stretching frequencies change rather more significantly, to a mean absolute error of 4.0 cm-1 and an RMS error of 7.4 cm-1.
Summarizing, B97-1/TZ2P is likely to be a useful tool for analysis of vibrational spectra (and verification of their assignments) of aromatic organic molecules in general and of the azabenzene series in particular.

### III.2 Pyridine

Pyridine being the simplest azabenzene (Figure 1b) and the closest to the parent molecule, we may anticipate similar accuracy as for benzene. As expected for this chemically important species, many experimental spectra are available, in both liquid and gas phases. Most of the experimental results and the latest experimental assignments are summarized by KlotsKlots . The computed and observed vibrational frequencies are presented in Table 3. As expected, the C-H stretching frequencies are not well described. Here, they are also heavily perturbed, and, considering performance for the corresponding bands in benzene, our method may not be sufficiently accurate to assist in the experimental assignment. Thus, although we will attempt to elaborate on the C-H stretching frequencies for most azabenzenes, the results are more tentative. Additionally, a small change in the original unperturbed fundamental frequencies will cause large changes in the perturbed frequencies. Nevertheless, the two asymmetric stretches $`\nu _{14}`$ and $`\nu _{15}`$ do not follow the general trend of being underestimated by 20–40 cm-1. While the perturbed $`\nu _{14}`$ is close to the experimental value, $`\nu _{15}`$ differs by 70 cm-1. Especially the latter appears too large to be accounted for merely by deficiencies in our DFT calculation. Here, the severe Fermi resonance seems to be responsible for this assignment, as its deperturbed value is at 3021 cm-1. This mode is resonating with (deperturbed frequencies given) $`\nu _{14}`$ at 3053 cm-1, $`\nu _4+\nu _{17}`$ at 3015 cm-1 and $`\nu _{16}+\nu _5`$ at 3054 cm-1, with the perturbed $`\nu _4+\nu _{17}`$ now appearing at 3023 cm-1. It appears that the latter value is more in line with experiment, and that perhaps this assignment might be more reasonable. Nevertheless, some caution is appropriate as the C–H harmonic stretching frequencies are not as well described by DFT as the remaining modes. Large basis set CCSD(T) harmonic frequencies would be helpful here, but would require inordinate amounts of CPU time.
Another picture emerges for the non C-H frequency modes. Here, we primarily compare to the medium resolution Raman vapor data of Klots (Klots2)Klots : their assignments seem to be in line with most other experiments, although they differ from the most recent data obtained by Partal et al.Kearley1 . Comparing to these latter inelastic neutron scattering (INS) data, however, amounts to comparing apples and oranges, as the INS data are based on further refinement of a DFT computed harmonic force field by maximizing agreement between simulated and observed INS spectral. The pseudo-harmonic frequencies from the refined force field correspond neither to true harmonic nor to true fundamental frequencies — in effect, they are neither fish nor fowl.
We can confirm the assignment of KlotsKlots  of $`\nu _{21}`$ to the lower value of 1053 cm-1. Difficult assignments seem to result from the Fermi resonances for both $`\nu _4`$ and $`\nu _{19}`$, since these are the only fundamentals which give errors of 10 cm-1 or larger. The deperturbed mode of $`\nu _4`$ at 1578 cm-1 resonates with $`\nu _9+\nu _{10}`$ at 1593 cm-1 resulting in perturbed modes at 1575 and 1596 cm-1. Klots may have misassigned the latter band to $`\nu _4`$ rather than $`\nu _9+\nu _{10}`$. $`\nu _{19}`$, on the other hand, seems to be very difficult to assign from experimental data because of its depolarized character. The problem is further exacerbated as $`\nu _{19}`$ is located at the shoulder of $`\nu _6`$. Although $`\nu _{19}`$ is involved in a Fermi resonance, it is probably not the source of the disagreement with, since its unperturbed frequency at 1241 cm-1 resonates with $`\nu _{10}+\nu _{12}`$ at 1282 cm-1, resulting in bands at 1237 and 1289 cm-1. With the exception of these two strongly perturbed bands ($`\nu _4`$ and $`\nu _{19}`$), the agreement between experiment and theory can only be described as stunning for bands other than C-H stretches. For the latter, probably only a full CCSD(T) force field can resolve the assignment. Even when including $`\nu _4`$ and $`\nu _{19}`$ (but excluding all C-H stretching frequencies), the mean absolute error for the computed values compared to the experimental data of KlotsKlots  is 3.6 cm-1 and the RMS error is 5.3 cm-1; without $`\nu _4`$ and $`\nu _{19}`$ they are reduced to 2.7 and 3.8 cm-1, respectively.
The double-harmonic infrared intensities are in good agreement with the B3LYP/cc-pVTZ valuesfirst  and in reasonable agreement with the experimental numbers. Even here, the C-H stretches differ, probably not only because of anharmonic contributions and Fermi resonances, but also because of the poor description of these modes by DFT. Still, the excellent performance seen for benzene results is repeated for pyridine.

### III.3 Pyridazine

Pyridazine (Figure 1c) has been of particular interest in the last couple of years Kearley2 ; Holly ; Boggs . A large body of experimental data is available, generally measured in the gas phase but when certain modes were unavailable, the authors of Ref.Holly ; Boggs  substituted their own liquid or solid phase measurements in order to get a full complement of frequencies. All of the spectra have been assigned with the aid of scaled Hartree-Fock, MP2, BLYP or B3LYP harmonic force fields using small basis sets. Some of them have their force fields fitted to match the experimental data. Despite the large amount of data, huge discrepancies exist, as shown in Table 4. This seems to be especially true for the out-of-plane modes where experimental assignments and values seem almost arbitrary. For $`\nu _{11}`$, for example, the experimental numbers range from 765 to 949 cm-1, and even the two most recent numbers appear at opposite ends of this range. These assignments have been done using different methods and scaling techniques, since no reliable theoretical data were available at the time.
The same problem with the C-H stretches that was encountered for benzene and pyridine occurs for pyridazine as well; the situation is further complicated since the experimental data differs and thus we cannot assign the frequencies of the experiment. Despite the discrepancies between various experimental numbers, all the C-H stretches appear plausible within the error range of our method.
As the INS data set dramatically varies from the remainder of the experimental data, and because it did not appear to be reliable for pyridine, it was excluded from our analysis, although it is reported in Table 4 for completeness.
Since such a large amount of experimental data is available, it is best to discuss each mode separately, starting with the in-plane modes.

* For $`\nu _3`$, all experiments except the first of Ref.Ozono  agree on an assignment to the 1570 cm-1 band. Our results, however, would seem to indicate that the assignment around 1555 cm-1 might be more plausible.
* The same occurs for $`\nu _4`$. Experimental values of Refs.Ozono ; Boggs  cluster around 1440 cm-1, with Refs. Holly ; Tucci  around 1415 cm-1. Our calculation clearly favors the former assignment.
* For $`\nu _5`$, significant differences between experiments of Refs.Ozono ; Holly ; Tucci  and the computed value of 1145 cm-1 can be found. The experimental results are thus untenable in light of this huge discrepancy of more than a hundred cm-1, and only Ref.Tucci  proposes an assignment of 1160 cm-1, which still appears to be on the high side.
* For $`\nu _6`$, most experiments have assignments around the computed 1157 cm-1; however, Ref.Boggs  assigned this mode to 1120 cm-1 because of their previous assignment. Our calculated $`\nu _5`$ and $`\nu _6`$ nearly coincide,
* For $`\nu _7`$, all experimental datasets are in agreement with each other and our calculations. Considering the generally small anharmonicities for this type of vibrations, the discrepancy of 40 cm-1 between the computed $`\omega _8`$ and the observed $`\nu _8`$ seems to be a bit on the large side. The experimental assignment may have been complicated by the band’s position in an IR band envelope going from 960 to 980 cm-1Boggs .
* As with $`\nu _5`$, the experimental assignment for $`\nu _9`$ of Vazquez et al.Boggs  differs from the other obtained fundamentals, and is the only one that can be confirmed by our calculations.
* For $`\nu _{16}`$, only Refs.Ozono ; Holly  differ from the computed values, while for $`\nu _{17}`$, the experimental assignment of Stidham and TucciTucci  both in the IR and the Raman phase appear doubtful. $`\nu _{18}`$ agrees nicely with all experiments.
* For $`\nu _{19}`$ and $`\nu _{20}`$, the same assignment problems that we experienced for $`\nu _5`$ and $`\nu _6`$ seem to have occurred; while most experiments assign values above 1100 cm-1 to $`\nu _{19}`$, only Vazquez et al.Boggs  seem to give the correct assignment. This results, however, in the value of $`\nu _{20}`$ thus ending up a bit on the low side, and only the value of Ref.Tucci  ends up close to our calculated number. The same seems to have happened to $`\nu _{21}`$, where only Ref.Boggs  is in line with our calculations. Hence, for the in-plane modes, the data set of Vazquez et al.Boggs  appears to be most reliable, excluding $`\nu _3`$ and $`\nu _6`$ (which appear to be dubious assignments) and perhaps $`\nu _8`$ and $`\nu _{20}`$.
* For the out-of-plane modes, the experimental assignment appears to be even more problematic. For $`\nu _{22}`$, all experiments differ by 20 cm-1, and are either found at 998 or 842 cm-1. Both assignments appear to be unlikely, since the harmonic B97-1 frequency is at 981 cm-1, which would put the fundamental too low for 998 and definitely way too high for assignment to the 842 cm-1 band.
* For $`\nu _{23}`$, all experimental assignments are around the computed 751 cm-1, while for $`\nu _{24}`$, all the experiments appear to yield assignments higher than our computed fundamental of 362 cm-1.
* Based on our data, all the $`a_2`$ symmetry modes ($`\nu _{10}`$ through $`\nu _{13}`$) should probably be re-examined, since several experimental results differ drastically from each other and from our calculations. A discussion of these modes is almost impossible, and with the exception of Refs. Boggs ; Ozono  for $`\nu _{13}`$, all experimental assignments lie beyond the likely error bars of the theoretical values.

On the whole, the pyridazine vibrational spectra definitely merit further investigation, as the many experimental and theoretical datasets available are considerably at variance with each other. Thus, it is impossible to give an error estimate for the method used based on this molecule. However if our computational results prove to be as accurate as for benzene and pyridine, the experimental spectra have to be reexamined. Based on this study, one might wonder whether the addition of more nitrogens or the N-N bond is causing the deterioration of the calculated values.

### III.4 Pyrimidine

Pyrimidine (Figure 1d), has been studied less in recent years. Notable are the IR experiments compiled by IRMMoomaw , the IR experiments of Billes et al.Holly , and the inelastic neutron scattering work of Navarro et al.Kearley3 . Here, we compare mainly to the IR experiments, since the INS data for neither pyridine nor pyridazine agree well with our computed values and the other experiments, for reasons outlined above. Nevertheless, for pyrimidine the INS data seem a lot closer to the IR data than for the previous two azabenzenes (Table 5). The values for the $`a_1`$ C-H stretches are in agreement with experiment, although this seems fortuitous. Otherwise, all in-plane modes are within 8 cm-1 of experiment, with the sole exception of $`\nu _{17}`$. Interestingly, both $`\nu _7`$ and $`\nu _9`$ undergo strong Fermi type 1 and 2 resonances; their resonance matrices are displayed in Table6 with their respective eigensolutions. For $`\nu _7`$, very small changes in the unperturbed fundamentals would result in the value ending up not at 1071 cm-1, but at the experimental assignment of 1065 cm-1. The assignment of the two resonating modes appears to be purely arbitrary. As for $`\nu _9`$, the resonating overtone of $`\nu _{24}`$ matches the experimental number exactly. Since both modes are in resonance, the overtone might have “borrowed intensity” (as described in Ref.Handyresonance ) from $`\nu _9`$, and thus the assignment.
When looking at the out-of-plane modes in Table 5, only $`\nu _{10}`$ and $`\nu _{20}`$ yield different results compared to the first set of experimental results. Both discrepancies have been mentioned before by the harmonic-only studyfirst , and $`\nu _{20}`$ has a very small intensity. Moreover, by using scaled HF frequencies, WibergWiberg  has suggested that the assignment for $`\nu _{10}`$ might also be incorrect. The IRMMoomaw  assignments for modes 5, 6, 13 and 21 appear more plausible than from Ref.Holly . Neglecting the problematic modes 10 and 20 and reassigning mode 9 to 677 cm-1, the errors, including the C-H stretches, are 6.3 (mean absolute) and 11.4 cm-1 (RMS), and without them are 4.1 and 5.3 cm-1, respectively. Thus this method again appears to be very reliable for predicting fundamental frequencies.

### III.5 Pyrazine

As with pyrimidine, only few experiments have been done for pyrazine (Figure 1e). The vibrational assignments are displayed in Table 7. In Ref.Holly , assignments were done in the gas phase for the IR active modes and in a melt for the Raman spectrum. Overall, the agreement is again very good for modes other than C-H stretches. If the previously mentioned tendency to underestimate the C-H stretches is taken into account, all assignments appear plausible, with the possible exception of the assignment of $`\nu _{11}`$ from Ref.Holly . It should be noted that all of the C-H stretches are perturbed by Fermi resonances. For the in-plane modes, especially $`\nu _{21}`$ appears to lie beyond the error bars of our method. It has been mentioned by the harmonic-only study in Ref.first  that this ‘Kekulé mode’ is problematic and it was concluded that this mode has significant multireference character, since it corresponds to the dissociation into 2 HCN + C2H2. However, hybrid density functionals are usually capable to describe nondynamical correlation to a certain extent, since for example the atomization energy of ozone is reasonably well reproduced. For this mode, the assignment of Ref.Marcos  appears to be out of question.
For all the other modes, most the experiments scatter only by about 5 cm-1, with this agreement suggesting that their assignments and values are pretty accurate. The out-of-plane modes are generally quite well described by theory. Note that the two $`a_u`$ modes since they are neither IR nor Raman active; for this reason they are not assigned in Ref.Holly . The INS values are somewhat disappointing for both frequencies, since the chief advantage of this method is the ability to predict such bands. Another discrepancy is the first $`b_{2g}`$ mode ($`\nu _9`$), although the second experiment of Ref.Holly  is closer to our values.
This leads to mean absolute and RMS errors compared to Ref.Holly  (Ref.Marcos ) of 7.8 (7.9) and 10.4 (11.1) cm-1 including the C-H stretches, and of 5.4 (5.1) and 6.9 (6.5) cm-1 when excluding them. If the problematic $`\nu _2`$ and $`\nu _9`$ are excluded, the mean absolute and RMS errors for the non C-H stretches reduces to 4.1 (4.1) and 5.4 (5.5) cm-1, respectively. Thus, the general RMS discrepancy of 5 to 7 cm-1 is obtained for pyrazine as well.

### III.6 1,3,5 Triazine (s-Triazine)

1,3,5-Triazine (Figure 1f) is the only azabenzene with a degenerate point group symmetry ($`D_{3h}`$). Because of this, the $`a_2^{}`$ modes ($`\nu _4`$ and $`\nu _5`$) are both IR and Raman inactive. The INS Kearley5  value for $`\mathrm{\_}nu_4`$ coincides exactly with our calculation (Table 8); the discrepancy of 124 cm-1 for $`\nu _5`$ is outlandish even for the INS data and this band is probably misassigned. The inelastic neutron scattering dataKearley1 ; Kearley2 ; Kearley3 ; Kearley4 ; Kearley5  are clearly inferior to the other experimental datasets. This is hardly surprising as this method relies on fitting and scaling a harmonic force field which is obtained from DFT in small split-valence basis sets. Already for the harmonics, this introduces errors on the order of about 50 cm-1. The error for the C-H stretches is expected to be even larger. It would be interesting to reanalyze their data based on the present anharmonic force fields, although this still would not resolve the problems associated with the C-H stretches, for which large basis set coupled cluster frequencies would be desirable. The experimental IR/Raman data of Daunt et al.Shurvell  and Lancaster et al.Colthup  are very similar to those of IRMMoomaw  and are not listed in Table 8. With the exception of the first $`e^{\prime \prime }`$ $`\nu _{12}`$ and the C-H stretches, which are again underestimated, all computed values are within 11 cm-1 of experiment Again, the errors are similar to the other azabenzenes; including the C-H stretches, the mean absolute error is 7.6 cm-1 and the RMS error 11 cm-1. Excluding the stretches (and $`\nu _{12}`$), these numbers reduce to 5.1 (3.4) and 7.5 (5.0) cm-1, respectively.

### III.7 1,2,3-Triazine

For 1,2,3-Triazine (Figure 1g), only one IR and Raman spectrum in KBr has been experimentally determinedScott : the assignment was assisted by scaled MP2/6-31G\* harmonic frequencies. The spectrum looks very similar to that of pyrimidine; even the same Fermi resonances are present.
At first glance at the spectra in Table 9, the agreement between theory and experiment is disappointing. For very few of the modes is there agreement between the spectra. However, the authors did not consider any Fermi resonances in the lower spectrum (although they noted that one might exist, involving $`\nu _{17}`$), and simply assumed the ordering of the fundamentals to be identical to that of the MP2/6-31G\* harmonics. This however leads to obvious misassignments. For example, $`\nu _6`$ and $`\nu _{18}`$ lie almost on top of each other, while $`\nu _{12}+\nu _{13}`$ borrows intensity from $`\nu _6`$ because of the Fermi resonance, as can be seen in Table 10. If the resonance were not as strong as computed — specifically, if the unperturbed fundamental were shifted only a few cm-1 towards higher values, the perturbed $`\nu _{12}+\nu _{13}`$, presently calculated at 1056 cm-1, might easily correspond to the band at 1064 cm-1, assigned to $`\nu _6`$ in Ref.Scott . The same actually applies to $`\nu _{20}`$, which has a strong Fermi resonance with $`\nu _9`$ \+ $`\nu _{13}`$, that has, however, been calculated at a lower value of 644 cm-1. We have also reassigned the first $`a_1`$ C-H stretch (mode 1), since the discrepancy between experiment and theory appears too high even for a C-H stretch. Needless to say, this mode also has a strong Fermi resonance with the $`2\nu _{15}`$ overtone, which has its largest component for the eigenvector with associated eigenvalue at at 3100 cm-1, again explaining the experimental value perfectly. The only other value which is still in question would be a small peak at 1597 cm-1, which might correspond to an impurity; a band was found that was assigned to acetylene, a fragmentation product of 1,2,3-triazine. The value of 318 cm-1, which has been reported for $`\nu _{13}`$ is actually just a scaled Hartree-Fock harmonic frequency.
Therefore, a dramatic change in the errors is obtained by reassigning the experimental spectrum. Including the C-H stretches in the error analysis, the mean absolute error decreases from 17.7 to 4.7 cm-1 and the RMS error from 27.9 to 6.1 cm-1. By excluding the C-H stretches, the mean absolute and RMS errors improve from 14.6 and 22.1 cm-1, respectively, to 4.1 and 5.2 cm-1. Thus, accuracy consistent with the preceding azabenzenes can be obtained following some reassignments in the experimental spectrum. This also corroborates our conclusion concerning pyridazine that neither substitution of C-H by N nor N-N bonds seem to be responsible for the discrepancies between experimental and computed vibrational spectra.

### III.8 1,2,4-Triazine

Because 1,2,4-triazine (Figure 1h) is highly unstable, only one “full” experimental spectrum has been measured as a liquid filmHennig , although more recently two high-resolution IR spectra have been recorded for four frequenciesPalmer1 ; Palmer2 . For the C-H stretches (Table 11), possibly $`\nu _1`$ and $`\nu _2`$ may have been swapped, since they both take part in a large resonance matrix block. Overall, ten frequencies and combination bands interact forming this large resonance block that include modes 1 to 3. Hence, it is not surprising that a correct assignment based merely on experimental data would be problematic. With this swap, all three C-H stretches are underestimated by the usual 10-30 cm-1. Only $`\nu _{11}`$ appears questionable in view of our results. However, $`\nu _9`$ has a Fermi resonance with the combination of $`\nu _{17}`$ and $`\nu _{21}`$, and the resonance, eigenvector and eigenvalue matrices are displayed in Table 12. The Fermi resonances displayed in these tables are similar to pyrimidine, 1,2,3-triazine and 1,2,4-triazine. Assuming that both of the Fermi resonances are slightly stronger than predicted, since $`\nu _{21}`$ is underestimated by 3 cm-1 compared to the high-resolution IR data, the new $`\nu _{17}`$ \+ $`\nu _{21}`$ could well end up lower than the predicted 1143 cm-1, explaining the value of 1136 cm-1 that would then not be assigned to any mode. The assignment of $`\nu _{11}`$ in the experiment would then correspond to $`\nu _{10}`$, in agreement with the calculated spectrum. The assignment of $`\nu _{13}`$ also appears to be incorrect.
Of the four modes obtained by high-resolution IR, the newer data for $`\nu _{12}`$ validates our computational value of 1044 cm-1 rather than the 1050 cm-1 predicted by the older experiment. On the other hand, the low-resolution IR value of 769 cm-1 for mode 19 is closer to the hi-res data compared to our predicted 779 cm-1. These new experiments show the usefulness of the theoretical value, since its resolution is apparently even comparable to that obtained by low-resolution IR data.
Without making any reassignments to the experimental spectrum, the mean absolute error from experiment is 13.6 cm-1, and the RMS error is 19.2 cm-1 including the C-H stretches. This appears to be quite large in comparison to the other azabenzenes. With the abovementioned suggested reassignments, these errors change to 7.5 cm-1 and 10.0 cm-1, respectively. Excluding the C-H stretches, we once again end up with a mean absolute error of 5.1 cm-1 and an RMS error of 5.8 cm-1.

### III.9 1,2,4,5-Tetrazine (s- Tetrazine)

For 1,2,4,5-Tetrazine (Figure 1i), CCSD(T) harmonic frequencies are available in the literatureLuthi . Unfortunately, they were calculated with all electrons correlated in a basis set (6-311G\**) that is only minimal in the inner-shell orbitals. The resulting errors in harmonic frequencies can easily exceed 20 cm-1 for small moleculesC4 , several times larger than the actual effect of neglecting core correlation (typically less than 10 cm-1 in HCNOF systemscore ). We have recomputed the CCSD(T)/6-311G\** frequencies correlating only valence electrons (Table 13). For the in-plane modes, differences with the all-electron calculations are quite minor (6 cm-1 or less). The out-of-plane modes, however, are drastically affected, up to 60 cm-1 (Table 13, especially the $`a_u`$ and the second b3u frequencies). This adds yet another stanza to the long litany of rejoinders in the literature (e.g.TaylorLNC1992 ) against the practice of correlating inner-shell electrons in basis sets unsuitable for the purpose.
We have recalculated the harmonic frequencies at the CCSD(T) level (frozen core) with basis sets of $`spdf`$ quality, specifically Dunning’s popular cc-pVTZ Dun89  and the Almlöf-Taylor atomic natural orbitalAlm87  basis set used in Ref.benzccsdt  for benzene. The CCSD(T)/cc-pVTZ and CCSD(T)/ANO4321 frequencies (Table 13) are in excellent agreement with each other, the largest difference being 6 cm-1 for the lowest frequency ($`\omega _{18}`$). (This is very unlike the case of benzenebenzccsdt , where the two $`b_{2g}`$ modes are hypersensitive to the basis set and differ significantly even between cc-pVTZ and ANO4321.) . The two corresponding modes in s-tetrazine display appreciable differences between 6-311G\* and cc-pVTZ but barely between cc-pVTZ and ANO4321.) In contrast, the CCSD(T)/6-311G\** frequencies differs significantly from both data sets, particularly for the two $`b_{2g}`$ modes (39 and 33 cm-1 w.r.t. ANO4321), followed by the lowest $`b_{2u}`$ mode (a.k.a. ‘Kekulé mode’, 27 cm-1) and the $`a_u`$ mode (25 cm-1, but a relative error of 7%). So even for a valence-only CCSD(T) calculation, the 6-311G\** basis set is insufficient, and the RMS deviation from the CCSD(T)/ANO4321 results, 16.4 cm-1 (17.3 when excluding the C-H stretching frequencies), is comparable to that of the much more cost-effective B97-1 calculations, 18.1 (15.1) cm-1.

Turning now to the B97-1/TZ2P harmonic frequencies, the most notable differences with the CCSD(T)/ANO4321 data are for the CH stretches (underestimates of 34 cm$`1`$ for both) and the Kekulé mode (overestimated by 37 cm$`1`$). Possibly, self-interaction error would adversely affectZiegler  the presently used functional’s description of the potential surface along the Kekulé mode, and it would be interesting how a self-interaction corrected functional would perform. Unfortunately no implementation of such a functional is available to the authors, let alone an implementation including analytical derivatives. Exclusive of this mode and the CH stretches, the RMS deviation between the CCSD(T)/ANO4321 and B97-1/TZ2P frequencies is about 11 cm-1, compared to just 4 cm-1 for benzene.

As expect, agreement between B97-1/TZ2P fundamentals and experiment is likewise compromised (Table 14). We note that s-tetrazine is both the least stable and the most ‘inorganic’ molecule of the series, and that it has a low-lying excited state at less than 2 eVLuthi . If we combine the CCSD(T)/ANO4321 harmonic frequencies with the B97-1/TZ2P anharmonic corrections, the picture brightens somewhat. Compared to the assignment of IRMMoomaw , the RMS deviation amounts to 9.8 cm-1 if the symmetric C–H stretch is excluded. The peculiarly large splitting of 76 cm-1 between IRM’s symmetric and asymmetric CH stretches is impossible to reconcile with any of our calculations, all of which suggest a very small splitting on the order of just 3 cm-1, in agreement with the earlier film IR and Raman study of Sigworth and Pace (SP)Sigworth . (Their band origin of 3089 cm-1 for the symmetric CH stretch is quite compatible with our calculations: IRM’s value of 3010 cm-1 was taken from single-vibronic-level fluorescence spectraInnes1 . An older gas-phase study by Franks, Merer, and Innes (FMI)Innes2  found both CH stretches at 3090 cm-1; the symmetric one in the IR, the antisymmetric one in the Raman spectrum.) Our calculations do not reveal a resonance interaction affecting $`\nu _1`$ that is severe enough to make a large CH symmetric/antisymmetric spllitting plausible. We hence conclude that $`\nu _1`$ of IRM is erroneous.

One other IRM assignment which is difficult to reconcile with our best calculations concerns the highest $`b_{3u}`$ mode (calculated: 902, IRM: 929 cm-1) for which the Franks, Merer, and InnesInnes2  value of 904 cm-1 nearly perfectly matches our calculation. It would appear that even the somewhat degraded performance, exhibited by our model for this molecule, still ought to be quite useful for resolving assignment issues or guiding high-resolution spectroscopic measurements.

## IV Conclusions

We have assessed the performance of modern density functional theory (particularly, B97-1/TZ2P) for the anharmonic vibrational spectra of a series of related medium-sized molecules. The C-H stretching frequencies are consistently underestimated by about 20-30 cm-1; disregarding them, the level of agreement with experiment that can be achieved is quite astonishing (on the order of 6 cm-1 RMS deviation for fundamentals). Somewhat poorer accuracy is achieved for pyridazine and particularly for s-tetrazine. For several systems (particularly 1,2,3-triazine), our calculations strongly suggest revised assignments of the observed frequencies. For pyridazine, unfortunately, the experimental results are mutually contradictory and our analysis inconclusive. For s-tetrazine, basically all predicted fundamentals agree less well with experiment; the more ‘inorganic’ character of the molecule may have adversely affected the performance of our calculations. Nevertheless, even here a RMS deviation of about 15 cm-1 for DFT and 10 cm-1 for the combined CCSD(T)/DFT results is obtained.
Overall, B97-1/TZ2P quartic force fields combined with second-order rovibrational perturbation theory shows great promise for the assignment of vibrational spectra of medium-sized organic molecules.

## V Acknowledgments

A. D. Boese is grateful for financial support from the Feinberg Graduate School. This research was supported by the Lise Meitner-Minerva Center for Computational Quantum Chemistry, of which J. M. L. Martin is a member, and the Helen and Martin A. Kimmel Center for Molecular Design.

## Supporting information

B97-1/TZ2P quartic force fields in normal coordinates of the molecules studied are available for download (in SPECTRO format) at the URL http://theochem.weizmann.ac.il/web/papers/azabenzenes.html.

Fig. 1:
The molecules investigated in this study, including benzene and the azabenzene series up to 1,2,4,5-tetrazine.


text:
# AC-Hopping Conductance of Self-Organized Ge/Si Quantum Dot Arrays

## I Introduction

We study Si samples with high-density ($`n=4\times 10^{11}`$ cm-2) arrays of Ge quantum dots (QD). According to Ref. , the low-temperature DC conductance of such samples is due to variable range hopping between different QDs. In such dense systems the long range Coulomb interaction is very important, mainly be-cause its influence on the electron density of states . Both the density of states and the DC conductance are sensitive to decay length of the electron states localized on the QD. Hence, it is tempting to find the electron localization length by an independent method. To fulfill this task we study attenuation of surface acoustic waves (SAWs) propagating near the QD array as a function of external magnetic field. SAW attenuation allows one to determine the AC conductance of the array, $`\sigma (\omega )`$, which depends on the localization length. The external magnetic field shrinks the electron wave function, and the consequent shortening of the localization length results in a decrease in the SAW attenuation.

We are aware only of one experiment , in which SAW attenuation in a GaAs/AlGaAs array of relatively large (250-500 nm) QDs was studied. In these samples QDs were fabricated using holographic lithography with subsequent ion etching. The authors interpreted their results assuming relaxational absorption within individual QDs . One can expect this mechanism to be very weakly dependent on magnetic field, so that the magnetic field dependence of the attenuation would not manifest itself in relatively weak magnetic fields. Consequently a dependence of the SAW attenuation on magnetic field at weak fields can be mostly ascribed to inter-dot transitions.

## II Experimental Results

We have measured variation of the attenuation coefficient, $`\mathrm{\Delta }\mathrm{\Gamma }=\mathrm{\Gamma }(\omega ,H)\mathrm{\Gamma }(\omega ,0)`$ and change of velocity of SAW $`\mathrm{\Delta }V/V=(V(H)V(0))/V(0)`$ \- in B-doped ”Ge in Si” dense ($`n=4\times 10^{11}`$ cm-2) QD arrays in magnetic field $`H`$ 6 T.

The samples were grown by MBE method on the (001) Si-substrate. Firstly, a 50 nm buffer layer of intrinsic Si-doped with B with $`N=2.4\times 10^{12}`$ cm-2 (6 holes per QD) was grown. Then a 5 nm undoped Si layer was grown, on top of which 8 Ge monolayers were placed. This structure was covered by a 30 nm i-Si layer. The self-organized Ge QDs had pyramidal shape with height of 15 $`\AA `$ and square 100 $`\times `$ 100 $`\AA ^2`$ base Fig. 1.

In our experiments the sample was pressed to a piezoelectric LiNbO3 crystal by a spring, and SAW propagated along the crystal surface Fig. 2. In such geometry the SAW is coupled to the holes only by electric fields, and a direct mechanical coupling turns out to be not very important . The SAW frequency was in the range 30-300 MHz, and the input intensity varied between 3$`\times `$10-6 and 3$`\times `$10-3 W/cm. Since $`\mathrm{\Delta }\mathrm{\Gamma }`$ is small even at $`H`$=6 T (about few $`\%`$), two methods were used to determine the SAW attenuation - direct measurement of the SAW amplitude $`U`$ at the receiver and comparison of this amplitude with the amplitude $`U_0`$ of another signal, which passed through the receiver’s amplifier avoiding the sample. In the second case the result is just the ratio $`U_0/U`$.

DC conductance was measured in this sample in the temperature interval 4.2-25 K without magnetic field. In this temperature interval it obeys the law $`\sigma ^{DC}`$($`\mathrm{\Omega }^1`$) = $`7.8\times 10^5exp[(282/T)^{0.5}]`$. This dependence is compatible with the variable range hopping in the Coulomb gap regime (Shklovskii-Efros mechanism ). Having in mind the values of the DC conductance, we expect that in the relevant frequency range the AC conductance of the sample is $`<10^7`$ $`\mathrm{\Omega }^1`$. At such values of conductance the screening of SAW electric field by the layer of QDs is not important, and the attenuation is just proportional to real part of the complex conductance, $`\mathrm{\Gamma }(\omega )Re\sigma _{xx}(\omega )`$.

The measured magneto-attenuation $`\mathrm{\Delta }\mathrm{\Gamma }`$ as a function of $`H`$ for different SAW frequencies is shown in Fig. 3. One can see that the attenuation decreases with magnetic field, $`\mathrm{\Delta }\mathrm{\Gamma }<`$0. The absolute value of $`\mathrm{\Delta }\mathrm{\Gamma }`$ is proportional to $`H^2`$ (Fig. 4).

To make the method useful for quantitative studies of the material one has to extract $`\mathrm{\Delta }\sigma (\omega )`$ and find its frequency and temperature dependences. For this purpose we employ the model of Ref. , which presents the system as a combination of semi-infinite substrate and sample divided by a vacuum clearance with thickness $`a`$. For $`\sigma <10^7\mathrm{\Omega }^1`$:

$`\mathrm{\Delta }\mathrm{\Gamma }={\displaystyle \frac{\mathrm{\Delta }\sigma A(q)qe^{2qa}}{2[(\epsilon _0+\epsilon _1)(\epsilon _s+\epsilon _0)(\epsilon _1\epsilon _0)(\epsilon _s\epsilon _0)e^{2qa}]^2}},`$ (1)
$`A(q)=8.68{\displaystyle \frac{K^2}{2}}8(\epsilon _0+\epsilon _1)\epsilon _0^2\epsilon _s,`$ (2)
where $`q`$ is the SAW wave vector, $`K^2`$ is the electromechanical coupling constant of the substrate (LiNbO3), $`\epsilon _1`$=51, $`\epsilon _0`$=1, $`\epsilon _s`$=12 are the dielectric constants of LiNbO3, vacuum and the sample, respectively. The clearance $`a=3\times 10^5`$ cm was determined using the well-known thin-film light interference method.

The dependence $`\mathrm{\Delta }\sigma (\omega )`$ at $`H`$=6 T and $`T`$=4.2 K, obtained using the aforementioned procedure, is shown in Fig. 5. The error was 30-40$`\%`$. One can conclude that there is no pronounced frequency dependence of $`\mathrm{\Delta }\sigma `$ in the frequency range 30-270 MHz.

To get an idea about temperature dependence of the magneto-attenuation we compare the ratio $`U_0/U`$ at frequency 87 MHz for temperatures 4.2 K and 1.5 K (Fig. 6). Decrease of this ratio with increase of $`H`$ means decreasing of the SAW attenuation. At $`T`$=1.5 K the SAW attenuation is practically magnetic field-independent. Different curves correspond to increasing and decreasing branches of the magnetic field cycle in the range 0-6 T.

As regards the measurements of the velocity of SAW in magnetic field this effect was small to be measured (relative change of velocity me can measure with accurate within $`5\times 10^5`$).

## III Discussion

We have observed negative SAW magneto-attenuation, which is proportional to $`H^2`$ in magnetic fields up to 6 T and in the temperature range 1.5-4.2 K. The real part of magnetoconductance, $`\mathrm{\Delta }\sigma `$, obtained from the raw data using the three-layer model , is also negative and proportional to $`H^2`$. It increases with temperature and almost frequency-independent.

Simple estimates show that the observed behavior cannot be allowed for taking into account only intra-dot transitions. Indeed, the inter-level distances in the small dots significantly exceed both $`\mathrm{}\omega `$ and $`kT`$. Thus we are left with two mechanisms: (i) tunneling or thermally-activated hopping between the states localized in different dots forming pairs; (ii) activation to the mobility edge, as in the case of the Coulomb-gap-mediated DC conductance.

In the first case, the theory (see Ref.  for a review) predicts a crossover from close-to-linear in frequency and temperature-independent to frequency-independent, but temperature-dependent $`\mathrm{\Delta }\sigma `$. This crossover takes place at $`\omega \tau 1`$, where $`\tau (T)`$ is the typical relaxation time for the inter-dot transitions. An-other feature of the inter-dot hopping is big ratio between imaginary and real parts of the complex conductance, Im$`\sigma (H,\omega )`$/Re $`\sigma (H,\omega )`$$``$1. The imaginary part of the magnetoconductance can be, in principle, extracted from the measured SAW velocity V. However, the variation of the velocity in magnetic field is too small to be measured at present time.

In the second case the ratio Im$`\sigma (H,\omega )`$/Re $`\sigma (H,\omega )`$$``$1, and the AC magnetoconductance should be close to the DC one. This behavior could be the case at low enough frequencies , when the distance between the relevant localized states, $`r_\omega `$ , is comparable with the hopping length, $`r_T`$, for the DC VRH conductivity. Crude estimations show, that in our experiment $`r_\omega `$ has indeed the same order of magnitude as $`r_T`$. Consequently, it seems to be difficult to discriminate between the processes at the mobility edge and the processes involving localized states.

## IV Conclusions

For the first time, AC magnetoconductance in a Ge-in-Si QD array is measured using the SAW technique. Mechanism of AC conductivity is probably a combination of diffusion at the mobility edge with hopping between localized states at the Fermi level.

###### Acknowledgements.

The work is supported by RFBR (Grants No. 01-02-17891 and 03-03-16536), MinNauki, Presidium RAN grants, NATO-CLG.979355 grants.