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# A simple model of DNA denaturation and mutually avoiding walks statistics

## I Introduction

Simple models of DNA thermal denaturation have attracted a lot of attention for a long time . Although it was pointed out rather early that excluded volume effects may be crucial in determining the order of the denaturation transition , it was only very recently that such effects were taken into account both at analytical and numerical level .

Even once accepted excluded volume effects as a key factor in determining the nature of the transition, one can still be interested in understanding how the relaxation of self-avoidance constraints influences the overall behavior of the system. As this can be done in different ways, learning in detail about the effects of different geometrical exclusion constraints can help in conceiving better models or more efficient approximations.

The main general aim of this paper is that of producing a contribution to the debate on these general issues. In particular we analyze the model of DNA denaturation recently introduced and studied by Garel, Monthus and Orland (GMO) . Among other things, we show that this model is a rather ideal context in which a recently proposed representation of DNA in terms of block copolymer networks  can be applied.

The Hamiltonian for the GMO model is :

$`H`$ $`=`$ $`{\displaystyle \frac{1}{2}}{\displaystyle \underset{i=1,2}{}}{\displaystyle _0^N}𝑑s\left({\displaystyle \frac{d\stackrel{}{r}_i(s)}{ds}}\right)^2+{\displaystyle _0^N}𝑑sV(\stackrel{}{r}_{12}(s))`$ (1)
$`+`$ $`g{\displaystyle _0^N}𝑑s{\displaystyle _0^N}𝑑s^{}\delta (\stackrel{}{r}_1(s)\stackrel{}{r}_2(s^{}))`$ (2)
where $`\stackrel{}{r}_1(s)`$, $`\stackrel{}{r}_2(s)`$ describe the conformations of the two strands as functions of the curvilinear coordinate $`s`$ and $`V(\stackrel{}{r}_{12}(s))`$ is the attractive interaction between homologous base pairs ($`\stackrel{}{r}_{12}(s)\stackrel{}{r}_1(s)\stackrel{}{r}_2(s)`$). The last term on the r.h.s. of Eq. (2) is due to excluded volume interactions, which act only between the two chains and not within a single chain. Thus the self-avoidance constraint is relaxed and each isolated strand follows a simple random walk (RW) statistics.

The authors of Ref.  simplified further the Hamiltonian (2) by approximating the excluded volume term by a long range interaction between the strands, which allows for an analytical solution of the problem. Within such approximation, the denaturation transition turns out to be of first order type , as in models where excluded volume effects are fully incorporated .

Our purpose here is to clarify further this point. We start from a description à la Poland - Sheraga (PS)  of the GMO model and use a series of exact results on reunion exponents of mutually avoiding walks, which show indeed that the denaturation transition is first order. More surprisingly, the transition turns out to be even sharper than that occurring in models where excluded volume effects are fully taken into account. This conclusion is corroborated by approximate analytical treatments of excluded volume effects due to loop-loop interactions and by a series of numerical results obtained for polymer lattice models in $`d=2`$ and $`d=3`$.

In the Poland - Sheraga (PS) model  the DNA chain is treated approximately as a sequence of non-interacting bound double segments and denaturated loops. Within this scheme the full partition function $`Z_N`$ for a chain whose constituent strands have lengths $`N`$, is factorized in terms of elementary partition functions for loops and segments (see Fig. 1). In the grand canonical ensemble, where a fugacity $`z`$ per lattice step is assigned, the total partition function reads :

$$Z(z)=\underset{N}{}z^NZ_N=\frac{V_0(z)}{1L(z)S(z)}$$
(3)
where $`L(z)`$ and $`S(z)`$ are the grand canonical partition functions for loops and double segments, respectively. The form of the numerator $`V_0(z)`$ depends on boundary conditions and is not interesting for our purposes. The crucial quantity is the loop partition function, which in the most general form reads :

$$L(z)=\underset{l}{}\frac{\left(\mu ^2z\right)^l}{(2l)^c}$$
(4)
where $`\mu `$ is the (non-universal) effective connectivity constant, while $`c`$ is a universal exponent. The order of the transition is related to the value of $`c`$ : At the transition temperature (which in the PS model corresponds to $`\mu ^2z1`$) loops are power-law distributed in size with probability $`P(l)l^c`$, thus their average size $`l=_llP(l)`$ is finite for $`c>2`$, implying a first order denaturation, while it diverges for $`1<c2`$ and the transition becomes continuous.

For self- and mutually avoiding strands $`c`$ was estimated analytically in an extended PS scheme , where excluded volume effects between a self-avoiding loop and the rest of the chain are approximately taken into account. This exponent was also obtained directly by Monte Carlo simulations  for polymer lattice models. The agreement between the analytical estimates and simulation results for $`c`$ is very good both in $`d=2`$ and $`d=3`$ .

In the next Sections we will present analytical and numerical estimates of the exponent $`c`$ for the GMO model. The former are based on the general theory of copolymer networks, which is briefly reviewed in the Appendix.

## II Mutually avoiding walks

A denaturated loop in the GMO model is formed by two mutually avoiding random walks of equal length $`l`$, with common origin and endpoint (see example of Fig. 2). The probability that two random walks, with common origin, meet for the first time after $`l`$ steps decays asymptotically as $`P(l)l^c`$ with :

$$c=d\nu 2\nu \eta _{11}^{(\mathrm{G})}.$$
(5)
Here $`d`$ is the dimensionality of the embedding space, $`\nu =1/2`$ for RWs and $`\eta _{11}^{(\mathrm{G})}`$ denotes the contribution of a vertex from which the two walks originate (see Fig. 2). We follow the notation of Ref.  and indicate with $`\eta _{f_1f_2}^{(\mathrm{G})}`$ the exponent associated to a vertex from which $`f_1`$ solid and $`f_2`$ dashed lines depart, at the gaussian fixed point, which is the relevant one for our purposes. At this fixed point solid and dashed lines do not interact with themselves, but they avoid the lines of the other group.

Figure 2, as well as Figs. 3-5 below, are examples of so called copolymer networks, i.e. networks whose constituents are polymers of different species. The relevance of these block copolymer networks for a description of denaturating DNA has been already stressed in the context of models with full excluded volume effects . A general network of this type may be made, for instance, by an arbitrary mixture of random and self-avoiding walks (SAWs). Any pair of these walks may either avoid, or be allowed to cross each other. As for the homopolymer case, the general entropic exponent for a network with arbitrary topology follows from those of the constituents vertex exponents (see Refs.  for details). The general rule to calculate the entropic exponent of a network is simple and it is reviewed in the Appendix. Restricting to the case in which all constituent polymers have the same $`\nu `$ exponent, one associates to each independent loop a factor $`d\nu `$ and to each vertex a factor $`\nu \eta `$, with $`\eta `$ the appropriate exponent which depends on the number of outgoing legs, and on their type. The generalization to an arbitrary mixture of polymer segments with distinct $`\nu `$’s, as for instance RWs and SAWs, is also possible.

Coming back to Eq. (5), the vertex exponent for one solid and one dashed line is known exactly in $`d=2`$ . Its value is $`\eta _{11}^{(\mathrm{G})}=5/4`$, which leads to $`c=2+1/4>2`$. In higher dimensions one has to resort to $`\epsilon `$ expansion renormalization group results. In $`d=3`$ resummation techniques yield $`\eta _{11}^{(\mathrm{G})}0.57`$ , which implies $`c2.07`$. Thus, both in $`d=2`$ and $`3`$ the reunion exponent is larger than the threshold value ($`c>2`$), which immediately implies a first order denaturation for the GMO model, within the PS picture of non-interacting loops and bound segments.

As a comparison we recall that for an isolated loop made by two self- and mutually avoiding strands the entropic exponent is :

$$c=d\nu .$$
(6)
For a SAW one has $`\nu =3/4`$ in $`d=2`$, which implies $`c=3/2`$, while $`\nu 0.588`$ in $`d=3`$, implying $`c1.76`$. Thus, within the PS picture, denaturation is a continuous transition ($`c<2`$) when full self- avoidance within a single loop is included .

It is also possible to go beyond the PS approximation in the GMO model, but it is already quite clear at this point that excluded volume effects between a single loop and the rest of the chain ”localize” even more the loops and $`c`$ can only increase. This can be shown explicitly for some simple geometries in which the loop is embedded. The calculations follow closely those of Ref.  for the model in which self - avoidance is fully included and are also briefly reviewed in the Appendix. We give here only the final results.

We consider the geometry shown in Fig. 3 in which a loop of length $`2l`$ is connected to two loops of length $`Nl`$ each. In the limit $`lN`$ the partition functions of the inner loop is still of the type of Eq. (4) and factorizes with the partition function of the rest of the chain . As explained in Appendix, the exponent $`c`$ is however modified:

$$c=d\nu \nu \eta _{22}^{(\mathrm{G})}.$$
(7)
In $`d=2`$ some care has to be taken in considering vertices, as the order of walks does matter. This is illustrated in Fig. 4 where the two possible distinct types of vertices with four outgoing lines, two solid and two dashed, are shown. For a vertex of type (a) more configurations are possible as neighboring lines of the same type are allowed to overlap. In (b), instead, the distinction between solid and dashed lines becomes irrelevant as neighboring lines avoid each other. In the latter case the lines form a vertex of four mutually avoiding walks (MAWs) . A vertex with $`L`$ outgoing MAWs, has an associated entropic exponent :

$$\eta _L^{(\mathrm{MAW})}=\frac{4L^21}{12}$$
(8)
Hence, for loops embedded in a geometry as in Fig. 3, and formed by vertices of type (b) one finds $`c=d\nu \nu \eta _4^{(\mathrm{MAW})}=3+5/8=3.625`$. Let us consider now vertices of type (a) for which we keep the notation $`\eta _{22}^{(\mathrm{G})}`$ to indicate the associated exponent. Using the prescriptions of Ref.  one has $`\eta _{22}^{(\mathrm{G})}=35/12`$ and thus from Eq. (7) $`c=2+11/242.46`$. Notice that stronger excluded volume effects (as for vertices of type (b)) imply a higher value for $`c`$, with a quite large difference between the two estimated values. We point out that, obviously, $`\eta _{11}^{(\mathrm{G})}=\eta _2^{(\mathrm{MAW})}`$ in all dimensions.

In $`d=3`$ the above subtleties do not occur. The vertex exponent $`\eta _{22}^{(\mathrm{G})}1.81`$ was estimated in Ref.  using $`\epsilon `$ expansions and resummation techniques. Thus, from Eq. (7), one obtains $`c2.40`$.

We consider now another geometry, where a loop is connected to two long double stranded segments, as illustrated in Fig. 5. Using the same method of Ref.  we find (see Appendix):

$$c=d\nu 2\nu \overline{\eta }_{1,2}$$
(9)
where with $`\overline{\eta }_{1,2}`$ we indicate the exponent associated to a vertex where one double, and two single stranded segments join. Notice that the double stranded segment is actually a self avoiding walk since, if it would overlap itself in some part, the mutual avoidance condition between the two constituent strands would be violated.

Again in $`d=2`$ one can use the techniques of Ref.  to find $`\overline{\eta }_{1,2}=27/16`$ which leads to $`c3.44`$. To our knowledge, there exists no field theoretical analysis for this type of vertices in higher dimensions, thus we are not able to make any predictions for $`c`$ in $`d=3`$, at present.

Table I summarizes the exponents found in the GMO model for an isolated loop ($`c^{(\mathrm{IL})}`$), for a loop interacting with other loops ($`c^{(\mathrm{LL})}`$), as in the geometry of Fig. 3, and for a loop interacting with double stranded segments ($`c^{(\mathrm{LS})}`$), as in Fig. 5. For the two dimensional case we reported both values of $`c^{(\mathrm{LL})}`$ corresponding to the loops formed by the two types of vertices of Fig. 4. We notice that, as anticipated above, the interaction with other parts of the chain has the effect of increasing the loop exponent $`c^{(\mathrm{LL})},c^{(\mathrm{LS})}>c^{(\mathrm{IL})}`$ as is the case for all other models studied so far . The first order character of the transition in the GMO model is therefore strengthened.

It is interesting to compare the exponents obtained in this paper with the corresponding ones for the model in which strands are fully self-avoiding (FSA). The latter, taken from Ref. , are given in Table I. The comparison between the two models indicates that the transition in the GMO model is generally sharper (higher $`c`$). This is always true with the exception of the exponent $`c^{(\mathrm{LL})}`$ in $`d=2`$ for vertices of the type of Fig. 4(a) for which we find $`c^{(\mathrm{LL})}2.46`$, for the GMO model, while $`c^{(\mathrm{LL})}2.69`$ in the FSA case. This is due to the fact that in the GMO model for the type of vertex considered excluded volume effects are not so pronounced as walks have considerable freedom to overlap.

## III Numerical Results

We performed a series of numerical calculations for a lattice version of the GMO model both in $`d=3`$ and $`d=2`$ (cubic and square lattices). We considered two random walks of length $`N`$, described by the vectors $`\stackrel{}{r}_1(i)`$ and $`\stackrel{}{r}_2(i)`$ ($`i=0,1,2\mathrm{}N`$) which identify the positions of the lattice monomers. The walks have common origin ($`\stackrel{}{r}_1(0)=\stackrel{}{r}_2(0)`$), and no specific boundary condition is imposed on the other ends. While each strand can overlap itself, mutual avoidance requires that $`\stackrel{}{r}_1(i)\stackrel{}{r}_2(j)`$ for $`ij`$. Overlaps at homologous points are however allowed ($`\stackrel{}{r}_1(i)=\stackrel{}{r}_2(i)`$); these correspond to a bound state of complementary base pairs, to which we assign an energy $`\epsilon =1`$. At sufficiently low temperature ($`T`$) the walks are fully bound and form an object obeying self-avoiding walk statistics.

We used the PERM  algorithm and computed $`P(l)`$ the probability distribution function (pdf) to find a loop of length $`2l`$ in the chain. While at low temperatures loops are exponentially distributed in size, at the critical point the pdf has an algebraic decay $`P(l)l^c`$, from which we can extract the exponent $`c`$ . Figure 6 shows a log-log plot $`P(l)`$ vs. $`l`$ in $`d=3`$ at the estimated critical point ($`T_c=0.5181(3)`$), for chains of lengths up to $`N=1280`$. A linear fit of the data yields $`c=2.55(5)`$, not far from the $`c^{(\mathrm{LL})}`$ given by Eq. (7) (see Table I). The result confirms that the transition in the GMO model is sharper than when self-avoidance is fully included. Indeed, in the latter case the most accurate numerical estimate of the loop exponent is $`c=2.18(6)`$ .

We consider next $`P^{}(r)`$, the probability that the distance between homologous points in the strands $`|\stackrel{}{r}_1(k)\stackrel{}{r}_2(k)|`$ equals $`r`$. This quantity was found to decay as a stretched exponential for $`r\mathrm{}`$ , from an analysis of the Hamiltonian of Eq. (2).

This conclusion is at odd with the algebraic decay of the loop pdf found here for the GMO model, and also in other similar models with a first order transition . For the numerical calculation of $`P^{}(r)`$ we registered all distances between homologous pairs along the chains $`|\stackrel{}{r}_1(k)\stackrel{}{r}_2(k)|`$, starting from $`k=1`$ and up to the highest $`k`$ for which the two strands are in contact ($`\stackrel{}{r}_1(k)=\stackrel{}{r}_2(k)`$). Figure 7 shows a plot of $`\mathrm{log}_{10}P^{}(r)`$ vs. $`\mathrm{log}_{10}r`$ at the transition temperature in $`d=3`$. We cannot fit the data with a stretched exponential decay, but by increasing the system size the data approach a power law decay $`P^{}(r)r^k`$ with $`k=2.1(1)`$. The fact that $`k>1`$ implies that the probability is normalizable. This is a confirmation that the transition is of first order type (see Ref. ). Notice however, that the algebraic nature of $`P^{}(r)`$ implies infinite moments $`r^n`$ starting from $`n=2`$. We conclude that the exponential decay found in Ref.  is an artifact of the approximation introduced.

We performed a series of calculations also in the two dimensional case. At the estimated critical temperature ($`T_c=0.5811(7)`$) we find, from the decay of the probability distributions $`P(l)`$ and $`P^{}(r)`$, the estimates $`c=2.95(5)`$ and $`k=3.0(1)`$, confirming the first order nature of the transition. Again denaturation happens to be sharper than in the case where self-avoidance is fully incorporated, for which $`c2.46`$ . In the PERM algorithm both types of vertices of Fig. 4 are generated, thus $`c`$ cannot be directly compared with any of the value obtained analytically in the previous section.

## IV Conclusion

In this paper we studied the model for DNA denaturation recently introduced by Garel, Monthus and Orland . Our analysis is complementary to that of Ref.  and it is based on the calculation of the exponent $`c`$ describing the algebraic decay of the probability of denaturated loop lengths at the critical point. Using exact results from mutually avoiding walks statistics we find that $`c>2`$ already for isolated loops, implying that the transition is of first order type. This conclusion is in agreement with the results of Ref. , but it is not based on the approximate treatments .

For some specific simple geometries in which a loop is embedded in the chain we provide analytical estimates of $`c`$, following ideas from the theory of polymer networks . These calculations show explicitly that $`c`$ increases with respect to the isolated loop value, i.e. the transition robustly maintains its first order character. More surprising is, at first sight, the fact that the denaturation in the GMO model is sharper than that occurring in models where excluded volume constraints are fully incorporated (higher $`c`$), as indicated by our analytical and numerical estimates of $`c`$ both in $`d=2`$ and $`3`$. This behavior can be explained by taking into account that the self-avoidance of the single strands somehow contrasts the excluded volume effects between each loop and the rest of the molecule. The result is that, when the single strand self-avoidance is relaxed, the loop sizes are further reduced, consistently with an increase of $`c`$.

It is somehow remarkable how results of the theory of block copolymer networks, which are relevant to issues like that of establishing a link between field theory and multifractal measures (see e.g. Ref. ), allow to draw reliable predictions on models of the denaturation transition of DNA.

There is another possibility of relaxing the self-avoidance which is somehow complementary to that of the GMO model. One can indeed neglect the mutual avoidance between the strands, while keeping self-avoidance within each stand. This possibility was studied in $`d=3`$ in Ref.  and the denaturation transition turns out to be continuous ($`c<2`$). Thus, relaxing the self-avoidance constraint in two different ways within the single loop, results in a softening (as in the latter example) or a sharpening (as in the GMO model) of the transition.

Finally, we also considered the probability distribution of the distances between homologous monomers of the two strands. We found that this quantity decays as a power law at the transition point, in disagreement with the stretched exponential behavior found in Ref. , which is probably an artifact of the approximation introduced there. The algebraic decay of various quantities at denaturation, even in the case of first order transitions, is a common feature of other similar models. Finding the appropriate treatment of the Hamiltonian (2), which provides power-laws decay at the transition point is still an open question.

## acknowledgements

Useful discussions with David Mukamel are gratefully aknowledged.

## Appendix

We review here some known results for entropic exponents of networks of arbitrary topology. We focus mainly on networks whose constituent polymers are all of the same type, and just briefly mention copolymer networks.

Let us consider a network made of self-avoiding walks, all avoiding each other, as the one shown in Fig. 8(a). Let $`N=_is_i`$ be the total length of the network, where each segment has length $`s_i`$. In the asymptotic limit $`N\mathrm{}`$, $`s_i\mathrm{}`$, the total number of configurations for the network scales as :

$$\mathrm{\Gamma }\mu ^NN^{\gamma _G1}f(\frac{s_1}{N},\frac{s_2}{N}\mathrm{})$$
(10)
where the factor $`\mu `$ is the effective connectivity constant for the walks (see e.g. Ref ) and $`f`$ is a scaling function. The universal exponent $`\gamma _G`$ depends only on the number of independent loops, $``$, and the number of vertices with $`k`$ outgoing segments $`n_k`$ as

$$\gamma _G=1d\nu +\underset{k}{}\nu \eta _kn_k$$
(11)
where $`\eta _k`$ are exponents associated to a vertex with $`k`$ outgoing legs. Such exponents are known exactly in $`d=2`$ from conformal invariance , while they have been obtained from renormalization group and resummation techniques in $`d=3`$ . We notice that it is also customary to use the definition $`\sigma _k\nu \eta _k`$.

This theory was recently applied to the denaturation problem . In this case one considers network geometries as that of Fig. 8(b), in which a loop of total length $`2l`$ is connected to two polymers of lengths $`N/2`$ each. Following the above notation one has $`=1`$, $`n_1=2`$ and $`n_3=2`$ and thus the total number of configurations scale as:

$$\mathrm{\Gamma }\mu ^NN^{\stackrel{~}{\gamma }1}f\left(\frac{l}{N}\right)$$
(12)
with $`\stackrel{~}{\gamma }=1d\nu +2\nu (\eta _1+\eta _3)`$. Now in the limit $`lN`$ one should recover the partition function for a self-avoiding walk of total length $`N`$ which has an entropic exponent $`\gamma =1+2\nu \eta _1`$. This requires that:

$$f(x)x^{2\nu \eta _3d\nu }$$
(13)
in the limit $`x0`$. Thus, loops of length $`l`$ embedded within a long chain of length $`N`$ ($`l`$) are distributed according to the probability $`P(l)l^c`$, with :

$$c=d\nu 2\nu \eta _3.$$
(14)
As second example we consider a loop of length $`2l`$ embedded between two long loops of total length $`2N`$, as depicted in Fig. 8(b). The total number of configurations is still given by Eq. (12) with $`\stackrel{~}{\gamma }=13d\nu +2\nu \eta _4`$, as the network has now $`=3`$ independent loops and two vertices with four outgoing legs, i.e. $`n_4=2`$. In the limit $`lN`$ one should find the partition function of two loops joined at a single vertex. Matching the scaling function in this limit yields

$$f(x)x^{\nu \eta _4d\nu }$$
(15)
for $`x0`$. One finds thus that loops are distributed according to the probability $`P(l)l^c`$, with :

$$c=d\nu \nu \eta _4.$$
(16)
Finally, this theory can be generalized to the case of networks with more than one type of polymer, as for copolymer networks. Eq. (11) can be generalized easily in the case that the constituting polymers have all the same metric exponents (for instance in the case of mutually avoiding random walks). The only difference is that now vertex exponents will not depend only on the number of outgoing legs, but also on the type of polymers forming the vertex and, in two dimensions, also on the order. For instance, for a network made of two types of polymers, which are random walks and mutually avoiding with a geometry of Fig. 3 one arrives to a $`c`$ exponent in the limit of an inner loop much shorter than the rest of the chain as given by Eq. (7), which is the copolymer network counterpart of Eq. (16). Notice that while for homopolymers $`\eta _2=0`$, in general a vertex with two outgoing polymers of different type will have a non-vanishing exponent (as is the case of the $`\eta _{11}^{(\mathrm{G})}`$ introduced in Fig. 2).

Finally if polymers constituting the inhomogeneous network will have different $`\nu `$ exponent, as for networks formed by a mixture of random and self-avoiding walks than Eq. (10) is still valid, but in a form involving the radii of gyrations $`R_i`$ of the constituent polymers, where $`R_is_i^\nu `$, for a segment of length $`s_i`$.


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# Cyclotron Resonance in Two-Dimensional Electron Single-Layers and Double-Layers in Tilted Magnetic Field

## 1 Introduction

The absorption of far-infrared radiation in two-dimensional electron layers subject to magnetic fields is used to determine the electron cyclotron mass. In a quasi-classical picture of the cyclotron resonance a magnetic field $`B_{}`$, perpendicular to the plane of the two-dimensional electron gas (2DEG), drives electrons with the cyclotron frequency $`\omega _c`$ along trajectories similar to the shape of a Fermi contour, but multiplied by $`\mathrm{}/(|e|B_{})`$, and rotated by $`\pi /2`$. The frequency $`\omega `$ of circularly polarized components of the electromagnetic wave either adds to or subtracts from $`\omega _c`$. The current $`\stackrel{}{𝒥}(\omega )`$ induced in the layer by the electric field $`\stackrel{}{}(\omega )`$ dissipates, and the corresponding power $`P`$ is expressed by

$$P=\frac{1}{T}_0^T\stackrel{}{𝒥}(\omega )\stackrel{}{}(\omega )𝑑t=\frac{1}{T}\underset{\alpha =x,y}{}_0^T\sigma _{\alpha \alpha }_\alpha ^2(\omega )𝑑t.$$
(1)
In this expression $`T=2\pi /\omega `$ is a period of the cyclotron motion and $`\sigma _{\alpha \alpha }`$ are the diagonal components of the conductivity tensor. The absorption power $`P`$ reaches maximum at the cyclotron resonance frequency, i.e. when $`\omega =\omega _c`$. The magnetic field at which the cyclotron resonance occurs, $`B_c`$, defines the cyclotron effective mass by $`m_c^{}=|e|B_c/\omega `$. For circular Fermi contours the cyclotron effective mass and the effective mass are identical, $`m_c^{}=m^{}`$. For the case of anisotropic effective mass $`m_x^{}m_y^{}`$ (an elliptic Fermi line) $`m_c^{}=\sqrt{m_x^{}m_y^{}}`$. In a quantum-mechanical picture, the electron states are quantized by the magnetic field $`B_{}`$ into Landau levels and transitions between adjacent levels are measured.

Here we present the theoretical study of the cyclotron resonance in symmetric 2D single-layers and double-layers subject to magnetic fields of general orientation. In this case the in-plane cyclotron mass becomes a function of both $`B_{}`$ and $`B_{}`$.

A parabolic quantum well with a confining potential $`V_{conf}(z)=m^{}\mathrm{\Omega }^2z^2/2`$ is used to model single-layer systems. Bilayer systems are represented by a pair of tunnel-coupled, strictly two-dimensional quantum wells, located at the distance $`d`$. These simple models allow to carry out most calculations analytically and are still able to capture the essence of physics of single-layer and bilayer systems. Results obtained for a single well are compared to experimental data of Takaoka et al .

Assuming the Landau gauge of the vector potential, $`\stackrel{}{A}=(B_{}y+B_{}z,0,0)`$, and a wave function in the form $`\psi e^{ik_xx}\phi (y,z)`$, the Hamiltonian can be written as

$$H=\frac{1}{2m^{}}(\mathrm{}k_x+eB_{}yeB_{}z)^2+\frac{p_y^2}{2m^{}}+\frac{p_z^2}{2m^{}}+V_{conf}(z).$$
(2)
Its eigenenergies are Landau levels degenerated in $`k_x`$ with a factor $`|e|B_{}/h`$. For $`B_{}=0`$ the variables $`y`$ and $`z`$ in the corresponding Schrödinger equation can be separated and for two lowest electron subbands denoted by an index $`j=0,1`$ we get two fans of Landau levels with the level index $`i=0,1,2,\mathrm{}`$.

In tilted fields, the in-plane component $`B_{}`$ influences strongly the orbital motion of electrons and modifies the structure of Landau levels corresponding to $`B_{}=0`$. In our symmetric systems a part of the Hamiltonian proportional to a product $`yz`$ is responsible for mixing of levels from different subbands when their level indeces $`i`$ differ by $`\pm 1`$. We denote the new modified fans of Landau levels by a subband index $`m=0,1`$ and the new levels by an index $`n=0,1,2,\mathrm{}`$. Note that in our symmetric systems the eigenfunctions $`\phi _{m,n}`$ of the Hamiltonian are either even or odd:

$$\phi _{m,n}(y,z)=(1)^{m+n}\phi _{m,n}(y,z).$$
(3)
## 2 Magneto-conductivity tensor

According to (1) only the “in-phase” parts of the diagonal components of the magneto-conductivity tensor are necessary to evaluate the dissipated power. We employed the Kubo formula to derive $`\sigma _{\alpha \alpha }`$ of single-layers and double-layers subjected to magnetic fields of general orientation. Since our aim is to study mainly the field-dependence of the energy levels $`E_{m,n}=E_{m,n}(B_{},B_{})`$ and of the transitions between them, we completely neglect the broadening of levels by scattering of electrons. With this simplifying assumption we get, as a response to the linearly polarized electromagnetic wave $`\stackrel{}{}(\stackrel{}{r},t)=2\stackrel{}{}\mathrm{cos}(\stackrel{}{q}\stackrel{}{r}\omega t)`$ in the dipole approximation, the conductivity in the form

$$\sigma _{\alpha \alpha }=\frac{2\pi e^2}{\omega }\underset{\mu ,\nu }{}f(E_\nu )|\mu |v_\alpha |\nu |^2\left[\delta (E_\nu E_\mu +\mathrm{}\omega )\delta (E_\nu E_\mu \mathrm{}\omega )\right].$$
(4)
Here $`f`$ is the Fermi-Dirac distribution function, $`\mu `$ or $`\nu `$ stands for a Landau level double-index $`m,n`$ and $`\alpha `$ denotes $`x`$ and $`y`$. The in-plane components of the conductivity $`\sigma _{xx}`$ and $`\sigma _{yy}`$ involve the matrix elements of

$$v_x=i\frac{\mathrm{}}{m^{}}\frac{}{x}\omega _{}y+\omega _{}z,v_y=i\frac{\mathrm{}}{m^{}}\frac{}{y},$$
(5)
the in-plane components of the velocity operator.

The single-layer with a parabolic confining potential represents a particularly simple example which can be solved analytically. In tilted magnetic fields, the cyclotron frequency corresponding to the perpendicular field configuration, $`\omega _{}=|e|B_{}/m^{}`$, and the frequency $`\mathrm{\Omega }`$ defining the separation of two subbands, are replaced by $`\omega _1`$ and $`\omega _2`$ given by

$$\omega _{1,2}=\frac{\sqrt{\omega _{}^2+(\omega _{}+\mathrm{\Omega })^2}\sqrt{\omega _{}^2+(\omega _{}\mathrm{\Omega })^2}}{2},$$
(6)
where $`\omega _{}`$ means $`\omega _{}=|e|B_{}/m^{}`$.

The eigenenergies $`E_{m,n}`$ read

$$E_{m,n}=\mathrm{}\omega _2(m+\frac{1}{2})+\mathrm{}\omega _1(n+\frac{1}{2}).$$
(7)
It follows from equations (4) and (5) that only intrasubband transitions, $`\delta m=0`$, between the neighbouring Landau levels, $`\delta n=\pm 1`$, or intersubband transitions, $`\delta m=\pm 1`$, between the Landau levels with the same index $`n`$, $`\delta n=0`$, are possible. Two different values of the cyclotron effective mass are connected with two processes, $`m_{c,1}^{}=|e|B_c/\omega _1`$ and $`m_{c,2}^{}=|e|B_c/\omega _2`$. Moreover, the conductivity can be written as a linear combination of

$`\sigma _1`$ $`=`$ $`{\displaystyle \frac{\pi e^2}{m^{}\omega }}{\displaystyle \underset{m,n}{}}\mathrm{}\omega _1(n+1)[f(E_{m,n})f(E_{m,n+1})][\delta (\mathrm{}\omega _1\mathrm{}\omega )\delta (\mathrm{}\omega _1+\mathrm{}\omega )],`$ (8)
$`\sigma _2`$ $`=`$ $`{\displaystyle \frac{\pi e^2}{m^{}\omega }}{\displaystyle \underset{m,n}{}}\mathrm{}\omega _2(m+1)[f(E_{m,n})f(E_{m+1,n})][\delta (\mathrm{}\omega _2\mathrm{}\omega )\delta (\mathrm{}\omega _2+\mathrm{}\omega )].`$
The components of the conductivity tensor read

$$\sigma _{\alpha \alpha }=W_{\alpha ,1}\sigma _1+W_{\alpha ,2}\sigma _2$$
(9)
where the weight factors $`W_{\alpha ,1}`$ and $`W_{\alpha ,2}`$ are different for $`\sigma _{xx}`$ and $`\sigma _{yy}`$

$`W_{x,1}={\displaystyle \frac{\omega _2^2\omega _t^2}{\omega _2^2\omega _1^2}},`$ $`W_{x,2}={\displaystyle \frac{\omega _t^2\omega _1^2}{\omega _2^2\omega _1^2}},`$ (10)
$`W_{y,1}={\displaystyle \frac{\omega _2^2}{\mathrm{\Omega }^2}}{\displaystyle \frac{\mathrm{\Omega }^2\omega _1^2}{\omega _2^2\omega _1^2}},`$ $`W_{y,2}={\displaystyle \frac{\omega _1^2}{\mathrm{\Omega }^2}}{\displaystyle \frac{\omega _2^2\mathrm{\Omega }^2}{\omega _2^2\omega _1^2}},`$
and $`\omega _t`$ is given by $`\omega _t^2=\omega _{}^2+\omega _{}^2`$.

The detailed description of the model of the bilayer systems can be found e.g. in . This model results in a pair of coupled differential equations for one-dimensional wave functions $`\phi _L(y)`$ and $`\phi _R(y)`$ localized in the left and right wells:

$`{\displaystyle \frac{\mathrm{}}{2m^{}}}\phi _L^{^{\prime \prime }}(y)+{\displaystyle \frac{m^{}\omega _{}^2}{2}}\left(y+{\displaystyle \frac{B_{}}{B_{}}}{\displaystyle \frac{d}{2}}\right)^2\phi _L(y)+t\phi _R(y)`$ $`=`$ $`E\phi _L(y),`$ (11)
$`{\displaystyle \frac{\mathrm{}}{2m^{}}}\phi _R^{^{\prime \prime }}(y)+{\displaystyle \frac{m^{}\omega _{}^2}{2}}\left(y{\displaystyle \frac{B_{}}{B_{}}}{\displaystyle \frac{d}{2}}\right)^2\phi _R(y)+t\phi _L(y)`$ $`=`$ $`E\phi _R(y).`$ (12)
Here, the orbit centres in individual wells are shifted due to the in-plane component of the magnetic field and the hopping integral $`t`$ describes the coupling of two two-dimensional electron layers.

We solve the coupled equations numerically and use the resulting eigenenergies and eigenfuctions to evaluate the cyclotron effective mass and transition matrix elements. The equation (3) helps to determine whether the Landau level belongs to the fan of a ground or an excited subband.

The above desribed approach is not appropriate when $`B_{}`$ is very small in comparison with $`B_{}`$. In such a case the quasi-classical description  should be employed. For small $`B_{}`$-components of magnetic fields it yields the same results as the quantum mechanical approach but it fails when both $`B_{}`$ and $`B_{}`$ are strong. Then the quantum mechanical approach must be used and the interpretation of cyclotron resonance experiments becomes more complicated as cyclotron effective masses depend on both $`B_{}`$ and $`B_{}`$.

## 3 Results and discussion

### 3.1 Two-dimensional electron single-layers

Within the parabolic-confinement approximation, the 2D electron single-layer system decouples into two harmonic oscillators with eigenfrequencies (6). The confinement frequency $`\mathrm{\Omega }`$ yields the subband separation in perpendicular magnetic field.

In tilted magnetic fields, if $`B_{}`$ is small ($`\omega _{}\mathrm{\Omega }`$), $`\omega _1`$ is determined mainly by $`\omega _{}`$ and the quantum number $`n`$ plays the role of the Landau band index, while $`\omega _2`$ reduces to $`\mathrm{\Omega }`$ and the quantum number $`m`$ represents the subband index. In high perpendicular magnetic fields ($`\omega _{}\mathrm{\Omega }`$) the roles of both indices are interchanged.

The $`B_{}`$-dependence of eigenenergies $`E_{0,n}`$ and $`E_{1,n}`$, $`n=0,1,2\mathrm{}`$ is shown in figure 2. The in-plane component of magnetic field increases the subband separation and changes the Landau-level structure. In tilted magnetic fields Landau-level mixing arises and not only intrasubband transitions between adjacent Landau levels of a single subband but also intersubband transitions between Landau levels with the same index and from different subbands are allowed. Figure 2 presents the field dependence of two different types of effective cyclotron masses associated with the eigenfrequencies $`\omega _1`$, $`\omega _2`$ and of weights of the intrasubband ($`W_{x,1}`$) and the intersubband ($`W_{x,2}`$) transitions are governed by the transition matrix elements which, similarly as $`m_c^{}`$ itself, strongly depend on both $`B_{}`$ and $`B_{}`$.

If 2D electron systems have only one occupied subband, various electron concentrations can be modelled by changing $`\mathrm{\Omega }`$, the higher the concentration, the narrower the well. We have found that wider parabolic wells are more sensitive to the magnitude of both magnetic field components than narrower (figure 4) and have shown (figure 4) that our model can reasonably fit the $`B_{}`$\- and $`B_{}`$-dependence of experimental data .

A convenient way to measure the cyclotron resonance in 2D electron systems is FIR optical magneto-absorption measured by Fourier transform spectrometer. The absorption process is accompanied by electron excitation from an occupied to an unoccupied level whereby the energy difference is an integer multiple of $`\mathrm{}\omega _c=\mathrm{}|e|B_{}/m_c^{}`$. At radiation energies equal to these differences the measured magnetoconductivity exhibits maxima.

The effective cyclotron mass can be calculated from the separation energy of Landau levels corresponding to allowed intrasubband or intersubband transitions. For fixed $`B_{}`$ and $`B_{}`$ Landau levels are equidistant (figure 6) and cyclotron effective masses connected with different transitions are identical (figure 6).

### 3.2 Two-dimensional electron double-layers

The coupling between quantum wells due to electron tunneling through the barrier removes the degeneracy of the energy spectrum and the lowest bound states of individual quantum wells form symmetric and antisymmetric pairs. In the perpendicular magnetic field the separation between symmetric and antisymmetric states is characterised by the interwell hopping energy $`2|t|`$. Results for 2D electron bilayers were calculated numerically. As follows from the Kubo formula (4), the diagonal components of the magnetoconductivity can be expressed in terms of a sum of dimensionless oscillator strengths $`f_{\alpha ,1}`$, $`f_{\alpha ,2}`$  where the index $`\alpha `$ denotes $`x`$ and $`y`$ as in the case of single-layer, and the indices 1 and 2 indicate intrasubband and intersubband transitions, respectively. Due to system symmetry, selection rules hold  and only transitions with nonzero oscillatory strength are allowed. These include intrasubband transitions $`\delta m=0`$, $`\delta n=\pm 1`$ and intersubband transitions $`\delta m=\pm 1`$, $`\delta n=0`$.

In what follows we concentrate on the lowest transitions from $`n=0`$ which are more pronounced than all other channels. Figures 8 and 8 show $`B_{}`$-dependence of eigenenergies calculated for a symmetrical double well structure and of oscillator strengths corresponding to the strongest permitted transitions in given system.

The Landau levels with high quantum numbers can be described both quasi-classically  and quantum-mechanically. Using our quantum-mechanical approximation for the case of slightly tilted field we have calculated spectrum of eigenenergies. With increasing in-plane component of magnetic field due to the process of electron transfer from the higher occupied antibonding subband to the lower bonding subband the separation energy between bonding and antibonding subbands grows until the antibonding subband is completely depopulated. Further growth of $`B_{}`$ leads to the degeneracy of Landau levels from the bonding subband as a result of the process is accompanied by complete suppression of interwell tunneling when electrons move in one of individual wells. Figure 10 shows the field-dependence of cyclotron effective masses calculated from eigenenergy spectrum presented on figure 10. The effective cyclotron masses corresponding to the highest antibonding subband decrease with increasing of the in-plane field, while cyclotron masses corresponding to the lowest bonding subband increase. The positions of singularities of cyclotron masses corresponding to the lowest bonding subband are related to the values of $`B_{}`$ at which coupled double quantum wells move to two decoupled electron layers. As the number of occupied levels depends on the Fermi energy, the increase in the electron concentration shifts the singularity position to the side of larger in-plane fields.

The field-induced electron-layer decoupling process, shown in figure 11, illustrates the aforementioned explanation. Wave function components of individual layers $`\phi _L(y)`$, $`\phi _R(y)`$ are shifted by the distance $`y_0=dB_{}/2B_{}`$ where $`d`$ is the distance between the potential minima in the left and the right well on the z-axis. The increase of the in-plane field is followed by a separation growth between $`\phi _L(y)`$ and $`\phi _R(y)`$. Moreover, with the increase of $`B_{}`$ wave function components of higher odd states loose their nodes and tend to coincide with the nodeless wave function components of lower even states.

## 4 Conclusion

To summarize, we have performed the theoretical study of the cyclotron resonance in 2D single-layers and double-layers subject to magnetic fields of general orientation to explain existing experimental results . For strong $`B_{}`$ and $`B_{}`$ the quantum-mechanical approach must be involved and $`m_c^{}`$ becomes a function of both components. We have calculated the field - dependence of the energy levels and transitions matrix elements between them. The Kubo formula was employed to derive diagonal components of magneto-conductivity tensor for both systems. The resulting conductivities are linear combinations of two 2D conductivities connected with intrasubband and intersubband transitions. Conclusions obtained for the model of the parabolic quantum well and for the model of coupled double-quantum wells are analogous. All results are obtained in a good qualitative agreement with experimental data.

## 5 Acknowledgements

This work has been supported by the Grant Agency of the Czech Republic under Grant No $`202/01/0754`$. The experimental curves in figure 4 are presented with kind permission of S. Takaoka.

## References


text:
# Band- and k-dependent Self-Energy Effects in the Unoccupied and Occupied Quasiparticle Band Structure of Cu

## I Introduction

Many-body exchange-correlation effects in the inhomogeneous interacting electron system of solids, reflected by the quasiparticle $`E(𝐤)`$ band structure observed in the experiment, are still far from complete understanding. The standard Density Functional Theory (DFT) accounts for these effects only in the ground state, yielding the static properties of the solids such as the charge density or the total energy. Of the DFT eigenvalues $`\epsilon (𝐤)`$, however, only the highest occupied one yields the correct excitation energy by a DFT analogue to the Koopmans theorem, while the others, strictly speaking, have no physical meaning as energy levels or excitation energies. Description of the quasiparticle excited states, created by external photon, electron, etc. impact, is by far more difficult (see, e.g., \[IX,IX\]). Their energies $`E(𝐤)`$ deviate from $`\epsilon (𝐤)`$ owing to the difference of the excited-state dynamic exchange-correlation potential, or the self-energy, from the ground-state static exchange-correlation potential $`V_{XC}`$ used in the DFT. The former is described by a complex energy- and $`𝐤`$-dependent non-local self-energy operator $`𝚺`$, whose imaginary part $`Im\mathrm{\Sigma }`$ describes the lifetime broadening of the excitation. Whereas for materials with strong local on-site correlations the excited-state many-body effects are usually described by model Hamiltonians, this approach cannot be extended to weakly correlated materials with long-range charge fluctuations. Only a few perturbational low-order approaches, such as the $`GW`$ approximation, are suggested for this case.

Cu has since long been believed to be a prototype weakly-correlated metal for which the DFT ground-state picture provides an accurate description of the excitation spectra (see, e.g., the review \[IX\]). Only recently, based on comparison of new angle-resolved photoemission (PE) data obtained under full control of the 3-dimensional wavevector $`𝐤`$ with state-of-art DFT calculations, we have demonstrated that the self-energy corrections $`\mathrm{\Delta }\mathrm{\Sigma }=E(𝐤)\epsilon (𝐤)`$ to the DFT in the valence band of Cu display a clear $`𝐤`$\- and band dependence, reaching values as large as 0.5 eV in the d-bands. These results gave a serious indication for the importance of self-energy effects even in such a supposedly simple metal as Cu. In fact, the previous misconception had arisen only due to errors of the early DFT calculations which accidentally matched $`\mathrm{\Delta }\mathrm{\Sigma }`$. Our preliminary $`GW`$ calculations have confirmed the general trends of the observed self-energy behavior. The most recent $`GW`$ calculations performed within the pseudopotential framework have yielded a striking agreement with the experimental valence band of Cu concerning the $`𝐤`$\- and band dependence of the $`\mathrm{\Delta }\mathrm{\Sigma }`$ shifts as well as their absolute values.

While the self-energy effects in the valence band can be studied using PE spectroscopy, the unoccupied states still remain largely unexplored. Conventional spectroscopies of the upper states using X-ray absorption or Bremsstrahlung phenomena provide only $`𝐤`$-integrated information such as the matrix element weighted density of states. The $`𝐤`$-resolving techniques such as inverse PE still involve two electron states and suffer from uncertainties in the surface-perpendicular wavevector $`k_{}`$. Only recently it was realized that in the energy region above the vacuum level the quasiparticle $`E(𝐤)`$ can be mapped under full control of the 3-dimensional $`𝐤`$ using Very-Low-Energy Electron Diffraction (VLEED) (see \[IX,IX,IX\] and references therein). As the PE final states are the time-reversed LEED states, this information can then be used in PE spectroscopy to achieve 3-dimensional mapping of the valence band $`E(𝐤)`$.

Here, we extend the self-energy analysis to the unoccupied states in the energy region from the vacuum level up to 40 eV above the Fermi level $`E_F`$ based on the VLEED experimental data. Contrary to a commonly accepted view, in this energy region the $`\mathrm{\Delta }\mathrm{\Sigma }`$ shifts also show a clear $`𝐤`$\- and band dependence. We support our findings by $`GW`$ calculations performed within the framework of linearized muffin-tin orbitals, which include the valence and core states on equal footing. We show that the $`\mathrm{\Delta }\mathrm{\Sigma }`$ anomalies correlate with the spatial character of the one-electron wavefunctions $`\varphi _𝐤`$, and endeavour to identify the essential physics of this. Our results on the valence band suggest that the $`GW`$ approximation underestimates the self-energy shifts due to the short-range charge fluctuations characteristic of the d-bands of Cu.

## II Experimental procedure and results

Our analysis employs the results of the recent VLEED and PE measurements performed on the Cu(110) surface. The information about the bulk band structure, reflected in the VLEED spectra, was insensitive to a slight oscillatory relaxation of this surface. This was confirmed by measurements on different surfaces as well as dynamical VLEED calculations.

Mapping of the unoccupied quasiparticle $`E(𝐤)`$ using VLEED (see \[IX,IX,IX\] and the references therein) is based on the fact that the diffraction process is connected with $`E(k_{})`$ along the Brillouin zone (BZ) direction determined by parallel momentum conservation (external $`𝐊_{}`$ = internal $`𝐤_{}`$). In particular, the extrema in the differential VLEED spectrum $`dT/dE`$ of the elastic electron transmission reflect the critical points (CPs) in the $`k_{}`$ dispersions of the bands whose Bloch wave $`\varphi _𝐤`$ efficiently couples to the incident plane wave. $`𝐊_{}`$ dispersion of the $`dT/dE`$ extrema, reflecting the CPs with $`k_{}`$ lying on a surface-parallel symmetry line of the BZ, yields then $`E(𝐤)`$ along this line resolved in the 3-dimensional $`𝐤`$. In our case the angle-dependent VLEED data with $`𝐊_{}`$ varying in the $`\overline{\mathrm{\Gamma }}\overline{Y}`$ azimuth of the surface BZ yielded $`E(𝐤)`$ along the $`\mathrm{\Gamma }X`$ line of the bulk BZ.

The direct mapping of the $`dT/dE`$ extrema reflects however the CPs in the quasiparticle $`E(𝐤)`$ near the surface, corresponding to $`\varphi _𝐤`$ excited by the VLEED beam and damped towards the crystal interior due to the finite electron lifetime, expressed by the electron absorption potential $`V_i=Im\mathrm{\Sigma }`$. Such $`E(𝐤)`$ is smoothed in $`k_{}`$ (the dispersions in $`𝐤_{}`$ remain nevertheless unsmoothed by virtue of the surface-parallel invariance of the VLEED process) compared to the quasiparticle $`E(𝐤)`$ in the bulk. The CPs appear as the points of extremal (inverse) curvature of the the $`k_{}`$ dispersions, and are intrinsically shifted from the corresponding CPs in the bulk $`E(𝐤)`$, recovered in the $`V_i=0`$ limit, within a few tenths of eV. To improve the accuracy of $`\mathrm{\Delta }\mathrm{\Sigma }`$ evaluation, based on comparison with the DFT implying $`V_i=0`$, we corrected our VLEED data from the $`V_i`$-induced shifts using a model calculation.

The model calculation employed the empirical pseudopotential method including $`V_i`$. $`E(𝐤)`$ and $`\varphi _𝐤`$ with complex $`k_{}`$ values were obtained by solving the Schrödinger-like equation

$`\left({\displaystyle \frac{\mathrm{}^2}{2m}}^2+V_{ps}iV_i\right)\varphi _𝐤=E\varphi _𝐤`$

where $`V_{ps}`$ is the pseudopotential. The VLEED spectra were calculated within the matching approach (see details in \[IX\]). In principle, matching calculations directly on top of the DFT calculations would be more straightforward, but this would require more complicated techniques such as the $`𝐤𝐩`$ expansion. In addition to the standard matching formalism, we included the surface barrier as an additional layer with a skewed-cosine like potential and performed matching on the vacuum-barrier and barrier-crystal planes. Compared to the step-like barrier, this improved the VLEED spectral structure energies by $`0.3eV`$. The shifts between the $`V_i=0`$ CPs and $`dT/dE`$ extrema, found in the model calculations, were then used to correct the experimental points back to the $`V_i=0`$ limit to reflect the bulk $`E(𝐤)`$. This procedure also compensated the slight shifts of the VLEED spectral structures caused by the surface barrier and overlap of spectral structures.

The obtained unoccupied quasiparticle $`E(𝐤)`$ is shown in Fig.1 compared to the DFT and $`GW`$ calculations (see below). The experimental points reveal only the bands with significant coupling to vacuum, and others are not seen. We omitted the points where strong multiple-band hybridization effects made it difficult to identify the CPs on the $`\mathrm{\Gamma }X`$ line reliably. The lower $`X_1`$-point measured by VLEED on the Cu(100) surface is also added.

Here we will also scrutinize our previous results on the valence band $`E(𝐤)`$ from \[IX\]. They are perfectly consistent with the whole body of previous experimental data compiled in \[IX\], but have a superior accuracy by virtue of employing a combined VLEED-PE method in which VLEED was used to achieve full control of the 3-dimensional $`𝐤`$. The experimental $`E(𝐤)`$ is shown in Fig.2 also compared with the calculations. The original data from \[IX\] was processed to include only the peaks relevant to the bulk states and compensate the lifetime induced intrinsic shifts of the PE peaks notable in the bottom of the $`sp`$-band ($`0.1eV`$). In principle, the accuracy of these data can be further improved by correcting for possible intrinsic shifts due to the surface and matrix element effects, but this would require demanding calculations within the one-step PE theory.

## III DFT and quasiparticle calculations

Our DFT calculations used the Generalized Gradient Approximation (GGA) for $`V_{XC}`$. For Cu the results were however almost indistinguishable from the LDA. A self-consistent full-potential linearized augmented plane wave (FLAPW) method implemented in the WIEN97 code was used, with the basis extended by local orbitals to reduce the linearization errors in the extended energy region of the unoccupied states. Spin-orbit coupling was also included. It should be noted that nowadays all state-of-art calculations on Cu agree within $`100`$ meV (at least in the valence band) which implies that the true DFT $`\epsilon (𝐤)`$ is achieved on this energy scale.The $`\mathrm{\Delta }\mathrm{\Sigma }`$ corrections to the DFT eigenvalues, given by the expectation values $`Re_\mathrm{\Omega }\varphi _𝐤^{}\left(𝚺V_{XC}\right)\varphi _𝐤𝑑𝐫^{}`$ with the integration over the unit cell $`\mathrm{\Omega }`$, were calculated in the framework of the $`GW`$ approximation. In this approximation the self-energy is given by

$`\mathrm{\Sigma }(𝐫,𝐫^{};\omega )={\displaystyle \frac{i}{2\pi }}{\displaystyle 𝑑\omega ^{}e^{i\eta \omega ^{}}G(𝐫,𝐫^{};\omega +\omega ^{})W(𝐫,𝐫^{};\omega ^{})}`$

In practical calculations, the Green function $`G`$ is approximated by a non-interacting one:

$`G(𝐫,𝐫^{};\omega )={\displaystyle \underset{𝐤}{}}{\displaystyle \frac{\psi _𝐤(𝐫)\psi _𝐤^{}(𝐫^{})}{\omega \epsilon _𝐤}}`$

In our case, $`\{\psi _𝐤,\epsilon _𝐤\}`$ are the LDA-DFT wavefunctions and eigenvalues. The screened interaction $`W`$ is given by

$`W(𝐫,𝐫^{};\omega )={\displaystyle 𝑑𝐫^{\prime \prime }v(𝐫𝐫^{\prime \prime })ϵ^1(𝐫^{\prime \prime },𝐫^{};\omega )}`$

where the dielectric matrix $`ϵ`$ is calculated within the random-phase approximation without employing the plasmon-pole approximation. The present $`GW`$ calculations employed one-electron calculations using the LDA exchange-correlation and the Linearized Muffin-Tin Orbitals - Atomic Sphere Approximation (LMTO-ASA) method. In contrast to the pseudopotential framework, this method allows to treat exchange-correlation with the core states on the same footing as the valence states. Details of the computation may be found in \[IX\]. The calculated $`\mathrm{\Delta }\mathrm{\Sigma }`$ values were added to the FLAPW eigenvalues whose computational accuracy at higher energies is better. The $`GW`$ calculations on Cu are technically rather demanding due to the presence of the $`d`$-states.

The results of the DFT and $`GW`$ calculations are also shown in Figs.1 and 2.

## IV Self-energy corrections

The unoccupied quasiparticle $`E(𝐤)`$ in Fig.1 deviate from the DFT results on the whole by $`1eV`$. However, the upper $`\mathrm{\Delta }_1`$-band displays an anomalously large shift by as much as $`2.8eV`$. Near $`\mathrm{\Gamma }`$ the bands are shifted also very unevenly. These anomalies, missed in the previous studies, have been resolved here for the first time by virtue of the single-state and $`𝐤`$-resolving nature of VLEED. Reported previously, a peculiar renormalization relative to the DFT is also observed in the valence band in Fig.2, where the shifts of the $`sp`$-band (up to $`+0.4eV`$ in its bottom) and the $`d`$-bands (about $`0.5eV`$) even differ in sign. In the bottom of the $`d`$-bands the deviations become smaller, which is due to hybridization of the $`d`$\- and $`sp`$-bands. Through the unoccupied and occupied states, the experimental shifts from the DFT are thus intriguingly band- and $`𝐤`$-dependent.

The deviations can have two sources. Firstly, the static $`V_{XC}`$ is not known exactly, and any DFT calculation has to resort to a reasonable approximation such as the GGA. However, the small difference between LDA and GGA results and the excellent description of ground-state properties suggest that for Cu this problem is insignificant. The second, therefore predominating, source is the excited-state self-energy effects due to the difference of the dynamic exchange-correlation $`𝚺`$ from the static one $`V_{XC}`$. Our comparison of the experimental quasiparticle and DFT energies thus directly yields $`\mathrm{\Delta }\mathrm{\Sigma }`$. The $`\mathrm{\Delta }\mathrm{\Sigma }`$ values in the $`X`$-point, corresponding in our experiment to $`𝐊_{}=0`$, are given in Table 1 compared to the $`GW`$ calculations.

Inclusion of the dynamic exchange-correlation within the $`GW`$ approximation are seen to vastly improve description of the experimental excitation energies. In the unoccupied states the agreement is almost ideal, in particular for the anomalous shift in upper $`\mathrm{\Delta }_1`$-band, with the only clear exception in the $`\mathrm{\Gamma }_2^{}`$ point. In the valence band the agreement is also excellent for the $`sp`$-band. In the $`d`$-bands the calculation correctly reproduces the sign of the $`\mathrm{\Delta }\mathrm{\Sigma }`$ shifts, although underestimates their magnitude. Interestingly, previous first-principles many-body calculations on Cu using formalisms other than $`GW`$ (see, e.g., \[IX\]) failed to reproduce the $`\mathrm{\Delta }\mathrm{\Sigma }`$ behavior even qualitatively.

The observed self-energy anomalies in the unoccupied bands should be taken into account in LEED surface crystallography (see, e.g., \[IX\]), which so far relied on a monotonous energy dependence of $`\mathrm{\Delta }\mathrm{\Sigma }`$. In our case, for example, the observed shifts of the VLEED spectral structures would be interpreted as due to a surface relaxation, but they are only due to the band- and $`𝐤`$-dependent self-energy behavior. The observed excellent relevance of the $`GW`$ approximation for the unoccupied states suggests to use it in LEED crystallography.

## V Mechanisms of the self-energy behavior

Although the observed self-energy behavior is well reproduced by the $`GW`$ calculations, their physical mechanisms remain obscured by the heavy computational machinery. We will now endeavour to identify the possible mechanisms, at least on a qualitative level.

### A Local-density picture

The observed anomalies in $`\mathrm{\Delta }\mathrm{\Sigma }`$ can be traced back to different spatial localization (SL) of the one-electron Bloch waves $`\varphi _𝐤`$, i.e. the distribution of their weight within the unit cell. Such a mechanism was originally suggested in \[IX\]. It assumes the local-density concept, i.e. neglects the non-locality of $`𝚺`$.

We start with a discussion of the $`\mathrm{\Delta }\mathrm{\Sigma }`$ behavior in the homogeneous electron gas. The dynamic exchange-correlation $`\mathrm{\Sigma }`$ as function of momentum $`k`$ and electron density $`n`$ was calculated for this model system by Hedin and Lundquist. From their data we derived $`\mathrm{\Delta }\mathrm{\Sigma }`$ as the difference of $`\mathrm{\Sigma }`$ to its value at the Fermi wavevector $`k_F`$, which, by the DFT analogue to the Koopmans theorem, is essentially the static $`V_{XC}`$. The resulting dependencies of $`\mathrm{\Delta }\mathrm{\Sigma }`$ on $`E/E_F`$ are shown in Fig.3 (left). The crucial parameter to determine their behavior is the electron density.

In real crystals the electron density is inhomogeneous. The electron gas plasmon dip in $`\mathrm{\Delta }\mathrm{\Sigma }`$ is damped (dashed line) by averaging over the varying local density $`n(𝐫)`$ and by interband transitions. Most importantly, as shown in Fig.3 (right), the effective electron density – and consequently $`\mathrm{\Delta }\mathrm{\Sigma }`$ – experienced by a one-electron wavefunction depends now on its spatial localization: if $`\varphi _𝐤`$ has large weight in the core region where $`n(𝐫)`$ is high, it will experience a large-density energy dependence of $`\mathrm{\Delta }\mathrm{\Sigma }`$, characterized by a strong $`\mathrm{\Delta }\mathrm{\Sigma }`$ repulsion from $`E_F`$. If $`\varphi _𝐤`$ expands well into the interstitial region with low $`n(𝐫)`$, it will experience a small-density dependence with its smaller $`\mathrm{\Delta }\mathrm{\Sigma }`$ repulsion from $`E_F`$. Such an SL mechanism goes beyond the usual wavefunction localization effect (see, e.g., \[IX\]) as not only the strength of the localization (measured by the bandwidth) matters but also the region of its localization.

In the valence band of Cu the SL mechanism has certainly some relevance (see also \[IX\]): The $`d`$-bands localized in the high-density core region experience large effective density and, reflecting the $`\mathrm{\Delta }\mathrm{\Sigma }`$ behavior in Fig.3, shift lower in energy, whereas the $`sp`$-band with its charge spread out into the low-density interstitial region experiences small effective density and shifts in the opposite direction. A qualitative support of this picture was obtained by calculating the effective densities $`\varphi _𝐤|n(𝐫)|\varphi _𝐤`$ (see \[IX\]), which well correlate with the experimental $`\mathrm{\Delta }\mathrm{\Sigma }`$ values both in the $`d`$\- and $`sp`$-bands. Exclusion of the core states from the total $`n(𝐫)`$ did not affect the correlation. However, the SL mechanism alone can not provide any quantitative description of the self-energy behavior mainly due to neglect of the non-locality of the $`𝚺`$ operator. Indeed, the corresponding calculation returned an unrealistic plasmon dip of $`\mathrm{\Delta }\mathrm{\Sigma }`$ in the unoccupied bands and, although properly reproducing the sign of the $`\mathrm{\Delta }\mathrm{\Sigma }`$ shifts in the valence band, severely underestimated their magnitude.

In the unoccupied states, the SL mechanism could not be reconciled with the experimental self-energy anomaly in the upper $`\mathrm{\Delta }_1`$-band even qualitatively unless we included into $`n(𝐫)`$ all core states down to the 1$`s`$ state having a binding energy of $`9`$ keV. Any significant effect of such a deep level on the dynamic exchange-correlation within the local density picture seems unrealistic. This hints on an extremely non-local mechanism of interaction with the core states, as we discuss below.

### B $`GW`$ picture

We will now analyze a connection between $`\varphi _𝐤`$ and the self-energy effects within the $`GW`$ framework, taking into account the non-locality of the $`𝚺`$ operator acting as $`𝚺\varphi _𝐤=_\mathrm{\Omega }𝚺(𝐫,𝐫^{})\varphi _𝐤\left(𝐫^{}\right)𝑑𝐫^{}`$ . First, we introduce a local quantity $`\mathrm{\Delta }\mathrm{\Sigma }\left(𝐫\right)`$ comprising local contributions to $`\mathrm{\Delta }\mathrm{\Sigma }`$, obtained by integrating out the non-locality of $`𝚺`$ as

$`\mathrm{\Delta }\mathrm{\Sigma }\left(𝐫\right)=\varphi _𝐤^{}{\displaystyle _\mathrm{\Omega }}\left\{𝚺(𝐫,𝐫^{})V_{XC}\left(𝐫\right)\delta \left(𝐫𝐫^{}\right)\right\}\varphi _𝐤\left(𝐫^{}\right)𝑑𝐫^{}`$

Integration of $`\mathrm{\Delta }\mathrm{\Sigma }\left(𝐫\right)`$ over the unit cell with the weight $`r^2`$ gives the total self-energy correction

$`\mathrm{\Delta }\mathrm{\Sigma }=4\pi {\displaystyle _\mathrm{\Omega }}r^2\mathrm{\Delta }\mathrm{\Sigma }\left(𝐫\right)𝑑𝐫`$

The calculated $`\left|\varphi _𝐤\right|^2`$, $`\mathrm{\Delta }\mathrm{\Sigma }\left(𝐫\right)`$ and $`r^2`$-weighted $`\mathrm{\Delta }\mathrm{\Sigma }\left(𝐫\right)`$ for the valence and unoccupied states in the $`X`$-point, obtained within the $`GW`$ framework, are shown in Fig.4. We note, firstly, that the total $`\mathrm{\Delta }\mathrm{\Sigma }`$ is always formed by a balance between positive local $`\mathrm{\Delta }\mathrm{\Sigma }\left(𝐫\right)`$ values in the core region and negative values in the interstitial region (which is seen better in the $`r^2\mathrm{\Delta }\mathrm{\Sigma }\left(𝐫\right)`$ curves). Such a behavior of $`\mathrm{\Delta }\mathrm{\Sigma }\left(𝐫\right)`$ is in fact general. Indeed, if $`𝚺`$ is assumed to be diagonal in the LDA Bloch basis as $`𝚺(𝐫,𝐫^{})=_𝐤\varphi _𝐤(𝐫)\mathrm{\Sigma }_𝐤\varphi _𝐤^{}(𝐫^{})`$, from the above equation we obtain

$`\mathrm{\Delta }\mathrm{\Sigma }\left(𝐫\right)\left(\mathrm{\Sigma }_𝐤V_{XC}\left(𝐫\right)\right)\left|\varphi _𝐤\right|^2`$

In the core region (small $`𝐫`$) the negative $`V_{XC}`$ blows up, forcing $`\mathrm{\Delta }\mathrm{\Sigma }\left(𝐫\right)`$ to become large and positive in this region. $`\mathrm{\Sigma }_𝐤`$, determined by the particular $`\varphi _𝐤`$, acts as a constant negative offset. In the interstitial region (large $`𝐫`$) $`V_{XC}`$ decreases and $`\mathrm{\Sigma }_𝐤`$ forces $`\mathrm{\Delta }\mathrm{\Sigma }\left(𝐫\right)`$ to become negative. In our case the off-diagonal elements of $`𝚺`$ are small, and such a pattern holds well for all states despite strong variations in the character of $`\varphi _𝐤`$.

At first glance, the SL mechanism seems to revive in this picture, with an amendment that the figure of merit is in fact the weight of $`\varphi _𝐤`$ in the core region rather than that in the high-density region (these two can somewhat differ). Indeed, if the weight of $`\varphi _𝐤`$ shifts into the core region, the positive contribution would increase and the quasiparticle level would shift higher in energy. However, this is much hampered by the $`\mathrm{\Sigma }_𝐤`$ offset, which is also sensitive to the character of $`\varphi _𝐤`$ in a highly involved manner.

In view of the limitations of the SL mechanism, another mechanism of the observed self-energy behavior can be suggested. Fig.4 shows that the valence and two unoccupied $`X_1`$-states are different from others in that their $`\varphi _𝐤`$ has a large $`4s`$ component, blowing up at the nucleus ($`𝐫=0`$). These – and only these – states experience an anomalous positive $`\mathrm{\Delta }\mathrm{\Sigma }`$ shift on top of the general trend that the $`\mathrm{\Delta }\mathrm{\Sigma }`$ repulsion from $`E_F`$ graually increases upon going away from $`E_F`$.

To extend this observation to other points in the BZ, we scrutinized the FLAPW calculations to determine the $`4s`$ projections (partial $`4s`$ charges) of $`\varphi _𝐤`$ inside the atomic spheres, which are given by coefficients in the expansion $`\varphi _𝐤=_{lm}A_{lm}u_{lm}\left(𝐫\right)Y_{lm}(\theta ,\varphi )`$. The calculated $`4s`$ projections are shown in Fig.5. Their comparison with the experimental results in Figs.1 and 2 demonstrates that the anomalous positive $`\mathrm{\Delta }\mathrm{\Sigma }`$ correspond everywhere to the $`\mathrm{\Delta }_1`$-states having large $`4s`$ character. Moreover, in Fig.6 we show the experimental $`\mathrm{\Delta }\mathrm{\Sigma }`$ values as a function of energy and the $`4s`$ projections for the whole $`\mathrm{\Gamma }X`$ line. Again, the anomalous positive $`\mathrm{\Delta }\mathrm{\Sigma }`$ on top of a regular energy dependence correlate everywhere with the large $`4s`$ character of $`\varphi _𝐤`$, with the only clear exception in the $`\mathrm{\Gamma }_{25^{}}`$-point.

The observed connection can not be explained within the above local picture, because the $`r^2`$-weighting cancels the contribution of $`\mathrm{\Delta }\mathrm{\Sigma }\left(𝐫\right)`$ from the nucleus region to the total $`\mathrm{\Delta }\mathrm{\Sigma }`$, see Fig.4. Moreover, other states such as $`X_5^{}`$ and $`X_4^{}`$, which have even more total weight in the high-density region than the states with the $`4s`$ character, can nevertheless not experience anomalous positive $`\mathrm{\Delta }\mathrm{\Sigma }`$. The observed connection can only manifest a non-local exchange-correlation effect, acting through the $`\mathrm{\Sigma }_𝐤`$ offset in the $`\mathrm{\Delta }\mathrm{\Sigma }\left(𝐫\right)`$ dependence.

In the following we propose a qualitative explanation for the above anomalous behaviour. Let us focus ourselves on the states $`X_5^{},X_3`$ and $`X_1`$ which have almost the same correlation energy $`\mathrm{\Sigma }_C`$, as can be seen in Table 2. It implies that differences in the self-energy shifts can only be due the differences in the exchange energy $`\mathrm{\Sigma }_X`$ and $`V_{XC}`$. The trend in

$`\mathrm{\Sigma }_X={\displaystyle \underset{𝐪}{}}{\displaystyle \varphi _𝐤^{}\left(𝐫\right)\varphi _𝐪^{}\left(𝐫\right)v(𝐫𝐫^{})\varphi _𝐪\left(𝐫^{}\right)\varphi _𝐤\left(𝐫^{}\right)𝑑𝐫𝑑𝐫^{}}`$

where $`𝐪`$ spans the occupied states, can be understood by analyzing the character of the states. Indeed, the $`X_5^{}`$-state, which has a large $`4p`$ character, has the smallest $`\mathrm{\Sigma }_X`$ among the three states. This is because the occupied states have very little $`4p`$ character, which makes the above exchange integral small. The $`X_3`$-state, on the other hand, has a significant $`3d`$ character, which gives a large exchange with the occupied $`3d`$ bands resulting in the largest $`\mathrm{\Sigma }_X`$. The $`X_1`$-state, the anomalous one, has a large $`4s`$ character but the occupied $`4s`$ valence states are plane-wave like so that $`\mathrm{\Sigma }_X`$ is somewhere in between those of the $`X_5^{}`$-state and $`X_3`$-state. The trend in $`V_{XC}`$ seems clear from the charge distribution of the states, with the $`X_3`$-state being the most localized inside the muffin-tin sphere. The physical picture arising from this qualitative analysis is that the $`X_1`$-state has an anomalously large shift because it has a large $`4s`$ character, which makes its exchange relatively small, and at the same time its charge distribution has a large weight inside the muffin-tin sphere where the exchange-correlation potential is deep, which makes $`V_{XC}`$ large. These two effects result in a large self-energy shift. We note that the amount of $`4s`$ character alone is probably insufficient to make a quantitative connection to the self-energy correction. For example, the lower unoccupied $`X_1`$-state is less anomalous although it has a large $`4s`$ character too. This can be understood from the fact that it has a significant $`3d`$ character (Fig.5), which increases the amount of exchange and reduces the self-energy shift. Such an effect of the $`3d`$ character is consistent with the negative $`\mathrm{\Delta }\mathrm{\Sigma }`$ shifts of the valence $`3d`$ bands. Moreover, our qualitative picture neglects the exchange-correlation with the core levels, while the recent $`GW`$ calculations suggest that the contribution of the $`3s`$ and $`3p`$ levels is significant.

The exchange contribution from the valence states, connected with the wavefunction character, explains therefore the self-energy anomalies on top of the SL mechanism. In the unoccupied states of Cu the exchange contribution becomes critical.

## VI Is the $`GW`$ approximation accurate for the localized orbitals?

The recent $`GW`$ calculation by Marini et al, performed within the pseudopotential framework, have demonstrated a good agreement with the experimental valence band of Cu both on the delocalized $`sp`$-band and the localized $`d`$-bands. They conluded that the $`GW`$ approximation, originally proposed to describe long-range charge oscillations, well extends to the localized orbitals and short-range correlations found in Cu.

Our $`GW`$ results are somewhat different however. They also demonstrate almost ideal agreement with the experiment on the delocalized bands such as the valence $`sp`$-band, but on the localized $`d`$-bands they tend to underestimate the negative $`\mathrm{\Delta }\mathrm{\Sigma }`$ shifts (see also Table 1). Interestingly, both calculations yield a wrong sign of $`\mathrm{\Delta }\mathrm{\Sigma }`$ in the bottom of the $`d`$-bands where they hybridize with the $`sp`$-band. Compared to the pseudopotential framework, our LMTO-ASA calculations have two fundamental advantages: 1) use of the true one-electron wavefunctions rather than pseudowavefunctions; 2) explicit inclusion of all core states, not only the $`3s`$ and $`3p`$ states as in \[IX\]. Another recent $`GW`$ calculation based on the full-potential LMTO  also yielded small $`\mathrm{\Delta }\mathrm{\Sigma }`$ shifts in the $`d`$-bands. The deviations from the experiment, remaining in the $`d`$-bands, would therefore indicate certain shortcomings of the $`GW`$ approximation in the description of localized orbitals and short-range correlations. However, any unambiguous conclusions on this point require further analysis, because the observed mismatch between different $`GW`$ calculations is comparable with their numerical accuracy.

## VII Other materials

Experimental $`𝐤`$-resolved data on the self-energy effects in the unoccupied bands of other materials is still scarce. In graphite we have found only a small and regular $`\mathrm{\Delta }\mathrm{\Sigma }`$ shift to higher energies (0.1 to 0.5 eV relative to the GGA-DFT) which however notably increased above a distinct absorption threshold at 35 eV. A similar situation has been found in NbSe<sub>2</sub>. Such an increase is not surprising, because the energy dependence of $`Re𝚺`$ is linked to that of $`Im𝚺`$ via the Kramers-Kronig relations. Interestingly, it was not reproduced by $`GW`$ calculations. In the valence band of graphite we have identified the SL mechanism to cause different $`\mathrm{\Delta }\mathrm{\Sigma }`$ shifts of the $`\sigma `$\- and $`\pi `$-states, having different overlap with the in-plane oriented valence electron density. In \[IX,IX\] it was speculated that widening of the valence band in graphite and other non-metals could result from electron localization in high-density regions, in agreement with the SL mechanism.

The unoccupied bands of Ni feature $`\mathrm{\Delta }\mathrm{\Sigma }`$ anomalies resembling those of Cu. It seems that they are typical for noble metals. The valence band of Ni (see, e.g., \[IX\] and references therein) is characterized by a narrowing of the $`d`$-bands ($`\mathrm{\Delta }\mathrm{\Sigma }`$ shifts towards $`E_F`$) which is opposite to Cu. This self-energy effect has a different origin - strong on-site correlations in the partially filled $`d`$-shell. The narrowing of the $`sp`$-band is however similar to Cu. Interestingly, in \[IX\] the $`𝐤`$-dependence of $`\mathrm{\Delta }\mathrm{\Sigma }`$ in the whole valence band was decomposed into constant contributions from the $`sp`$\- and $`d`$-bands whose weight was determined only by the band hybridization. Narrowing of delocalized bands has also been observed for simple metals like Na.

## VIII Conclusion

Excited-state self-energy effects in the unoccupied and valence band electronic structure of Cu were investigated. The unoccupied quasiparticle bands in the energy region up to 40 eV above $`E_F`$ are for the first time mapped under full control of the 3-dimensional $`𝐤`$ using VLEED. They demonstrate, similarly to the valence bands, a significant band- and $`𝐤`$-dependence of the $`\mathrm{\Delta }\mathrm{\Sigma }`$ self-energy corrections to the DFT. The observed $`\mathrm{\Delta }\mathrm{\Sigma }`$ behavior in the unoccupied and valence bands correlates with the spatial localization of the one-electron wavefunctions in the unit cell, and with their behavior in the core region expressed by the $`4s`$ and $`3d`$ projections. These effects are described, correspondingly, by the spatial localization mechanism based essentially on the local-density picture, and by the non-local exchange interaction with the valence states. In the unoccupied bands of Cu the latter is particularly important. Our $`GW`$ quasiparticle calculations performed within the LMTO-ASA framework yield almost ideal agreement with the experiment on the delocalized bands such as the unoccupied and valence $`sp`$-bands, but on the localized $`d`$-bands they underestimate the $`\mathrm{\Delta }\mathrm{\Sigma }`$ shifts. This may indicate certain limitations of the $`GW`$ approximation applied to the localized orbitals and short-range correlations. The observed band- and $`𝐤`$-dependent self-energy effects in the unoccupied bands have an important implication in LEED studies of the surface crystallography.

## IX Acknowledgements

We thank R. Feder for valuable discussions. This work was supported by Deutsche Forschungsgemeinschaft (grant Cl 124/5-1).