# Correlation–enhanced Friedel oscillations in amorphous alloys and quasicrystals

## I introduction

A large class of noble–polyvalent metal alloys exhibit a crystalline to amorphous transformation (CAT) as a function of the polyvalent metal content. There are several experimental indications for the amorphous phase being stabilized by the Hume–Rothery (HR) mechanism, i.e. by forming a structure–induced pseudogap in the electronic density of states (DOS) at the Fermi level $`\epsilon _F`$. The experimental evidence  includes the observation of a pronounced pseudogap, a maximum of the electrical resistivity at the CAT, and the coincidence of the atomic spacing $`a`$ with the Friedel wave length $`\lambda _F=\pi /k_F`$ near the CAT, where $`\mathrm{}k_F`$ is the Fermi momentum. Very similar behavior is found in icosahedral (i) quasicrystals . The conjecture of a HR–like stabilization mechanism is strongly supported by detailed theoretical studies both for amorphous  and for quasicrystalline  systems, although there is also the possibility of entropic stabilization . The fact that in the amorphous state the above–mentioned structural matching is observed over distances of up to $`5\lambda _F`$ has lead to the assumption that these remarkably long–range correlations are induced by the ions being bound in the minima of the potential formed by the Friedel oscillations (FO) around an arbitrary central ion.

However, several experimental puzzles have remained unexplained: (1) At finite temperature $`T`$ and also in the presence of disorder the impurity–averaged FOs are exponentially damped due to the spread of the Fermi momentum over a width given by $`T`$ and the inverse elastic mean free path, respectively. Hence, the stability of amorphous alloys at elevated $`T`$, in particular their intermediate–range structural correlations, are difficult to explain by the conventional FOs. (2) In all HR–systems, invariably the amorphous state is thermally most stable just at the CAT . (3) In the amorphous state the ionic positions are systematically shifted compared to the minima of the Friedel potential of a free electron sea . The experimental findings (1)–(3) raise the question of a systematical, composition dependent enhancement and phase shift $`\phi `$ of the FOs, where $`\phi `$ varies from $`\phi \pi `$ deep inside the amorphous phase to $`\phi =\pi /2`$ at the CAT. As shown below, these problems can be explained by one single quantum effect.

## II Theory

In amorphous alloys the electronic motion is diffusive instead of ballistic. Since diffusion, as a dissipative process, is difficult to include in an ab initio calculation, we here choose a Feynman diagram technique, where diffusion arises in the formalism by averaging over all random configurations of the system. The Nagel–Tauc condition $`2k_F2\pi /ak_p`$ implies strong electronic backscattering off local ion clusters. It has been shown  that this not only generates a pseudogap but at the same time leads to a substantial enhancement of the electron transport or density relaxation rate $`\tau ^1`$ over the quasiparticle decay rate $`\tau _{qp}^1`$. This is evidenced experimentally by the anomalously small electrical conductivity, $`\sigma =ne^2\tau /m^{}`$. Thus, we have as a generic feature of the amorphous state: $`\tau ^1\tau _{qp}^1`$.

We now turn to the calculation of the electron density distribution $`\rho (r)`$ around an ion embedded in the disordered electron sea. One does not expect a single ion to generate a sizable phase shift of the FOs at distances $`r>a`$, $`\rho (r)\text{cos}(2k_Fr\phi )/r^3`$, since it is equal to the electron backscattering phase off that ion, which is small unless $`\epsilon _F`$ is close to an internal resonance. Instead we consider quantum effects due to disorder and Coulomb interaction and assume, for simplicity, a point–like ion charge and a quadratic band $`\epsilon _k=\mathrm{}^2k^2/2m^{}`$. In a diffusive electron system screening is inhibited, so that the effective Coulomb interaction $`v_q^{eff}(z,Z)`$ between electrons with complex frequencies $`z`$ and $`z+Z`$ acquires a long–range, retarded part ,

$`v_q^{eff}(z,Z)={\displaystyle \frac{v_q}{ϵ^{RPA}(Z,q)}}\mathrm{\Gamma }^2(z,Z,q),v_q={\displaystyle \frac{4\pi e^2}{q^2}},`$ (1)   
where $`ϵ^{RPA}(Z,q)=1+2\pi i\sigma /(Z\text{sgn}Z^{\prime \prime }+iq^2D)`$ is the disordered RPA dynamical dielectric function and the diffusion vertex, defined in Fig. 1 a), is

$`\mathrm{\Gamma }(z,Z,q)=\{\begin{array}{cc}\frac{i/\tau \text{sgn}Z^{\prime \prime }}{Z+iq^2D\text{sgn}Z^{\prime \prime }}\hfill & z^{\prime \prime }(z+Z)^{\prime \prime }<0\hfill \\ 1\hfill & \text{otherwise.}\hfill \end{array}`$ (4)   
$`D=1/3v_F^2\tau `$ and <sup>′′</sup> denote the diffusion constant and

the imaginary part, respectively. The long–range nature of $`v_q^{eff}`$ originates from the diffusion pole of $`\mathrm{\Gamma }`$. In order to calculate its effect on the FOs, one must consider contributions to the polarisation $`\mathrm{\Pi }(0,q)`$ where $`\mathrm{\Gamma }(z,Z,q^{})`$ enters at $`Z,q^{}0`$, although $`\mathrm{\Pi }(0,q)`$ is evaluated at large external momenta $`q2k_F`$. The leading singular contribution arises from the quantum correction shown in the second diagram of Fig. 1 b). For amorphous metals ($`\tau ^1\tau _{qp}^1`$, see above) it is evaluated as ,

$`\mathrm{\Pi }^{(1)}(0,q)=C(\epsilon _F\tau ){\displaystyle _{\epsilon _F}^{\epsilon _F}}\text{d}\nu {\displaystyle \frac{1/(4T)}{\text{cosh}^2\frac{\nu }{2T}}}{\displaystyle \frac{\text{sgn}(x1)}{\sqrt{|x1|}}},`$ (5)   
where $`x=x(\nu )=(q/2k_F)/\sqrt{1+\nu /\epsilon _F}`$ and $`C(\epsilon _F\tau )=0.343[2m^{}k_F/(2\pi \mathrm{})^2]/(\epsilon _F\tau )^{7/2}`$. The first term of Fig. 1 b), $`\mathrm{\Pi }^{(0)}(0,q)`$, corresponds to the Lindhard function, where $`\mathrm{\Gamma }`$ contributes only a nonsingular factor of $`𝒪(1)`$. It is seen from Eq. (5) that for $`T=0`$, $`\mathrm{\Pi }^{(1)}(0,q)`$ exhibits a powerlaw divergence $`\text{sgn}(q2k_F)/|q2k_F|^{1/2}`$ at $`q=2k_F`$. Although at finite $`T`$ or $`\tau _{qp}^1`$ the divergence of $`\mathrm{\Pi }^{(1)}(0,q)`$ is reduced to a peak, the inverse dielectric function $`1/\epsilon (q)=1/(1v_q\mathrm{\Pi }(0,q))`$ still has a $`q=2k_F`$ divergence at a critical transport rate $`\tau _c^1(T)`$ even for non–zero single–particle relaxation rate $`\tau _{qp}^1<\tau ^1`$ and at finite $`T`$. The parameter $`\tau ^1`$ is varied experimentally by changing the composition of the alloy.

## III Discussion and comparison with experiments

Fourier transforming $`11/\epsilon (q)`$ to obtain $`\rho (r)`$  shows that for incomplete Fermi surface–Jones zone matching, i.e. small $`\tau ^1`$, the quantum corrections generate density oscillations $`\rho ^{(1)}(r)\text{cos}(2k_Fr)/r^3`$, which overcompensate the conventional FOs, implying a phase shift of $`\phi =\pi `$ . As $`\tau ^1\tau _c^1`$, the increasing $`2k_F`$ peak of $`1/\epsilon (q)`$ leads in addition to density oscillations $`\rho ^{(1)}(r)\text{sin}(2k_Fr)/r^2`$, so that in the vicinity of $`\tau _c^1`$

$`\rho (r){\displaystyle \frac{\text{cos}(2k_Fr)}{(2k_Fr)^3}}+A(\tau ^1){\displaystyle \frac{\text{sin}(2k_Fr)}{(2k_Fr)^2}},`$ (6)   
with $`A(\tau ^1)0.343\pi (1\tau ^1/\tau _c^1)^{1/2}`$. The exponent $`1/2`$ is characteristic for diffusive behavior. Thus, the FOs are shifted by $`\phi =\pi \text{tan}^1[2k_FrA(\tau ^1)]\pi /2+1/(2k_FrA)`$, i.e. the diverging Friedel amplitude necessarily goes hand in hand with $`\phi =\pi /2`$. Note that, in contrast to the conventional FOs, this divergence is robust against damping due to finite $`T`$ or disorder. The point where the amplitude $`A`$ diverges should be identified with the CAT, since at this point the fluctuations of the Friedel potential also become large, allowing the system to find its crystalline ground state. This resolves in a natural way the problems (1)-(3) mentioned in the introduction.

For a direct comparison with experiments the control parameter of the theory, $`\tau ^1`$, must be translated into a parameter, which is experimentally accessible: It follows from the scattering theory  that $`\tau ^1=\tau _o^1+\gamma S(2k_F)`$, where the peak of the ionic structure factor $`S(q=2k_F)`$ controls the backscattering amplitude, $`\gamma `$ is a constant, and $`\tau _o^1`$ is an offset due to momentum independent scattering. $`S(2k_F)`$ in turn is proportional  to the measured, structure–induced suppression of the DOS $`N(\epsilon _F)`$ at the Fermi level, $`1N(\epsilon _F)/N_o(\epsilon _F)1g`$, compared to the free electron gas, $`N_o(\epsilon _F)`$. The resulting fit of the crystallization temperature $`T_c`$ is shown in Fig. 2, where the contribution to the stability coming from the pseudogap formation is assumed to be linear in $`(1g)`$ (dashed line). The inset shows the calculated phase shift $`\phi `$ and the measured shift of the atomic nearest neighbor position relative to the position of the first conventional Friedel minimum, $`a_o=\pi /k_F`$. Note that there is no adjustable parameter in $`\phi `$. The general behavior of the shift is well explained by the theory; however, the experimental data approaches $`\phi =\pi /2`$ faster than predicted. This might be attributed to the fact that, as seen from the discussion after Eq. (6), the higher–order Friedel minima approach $`\phi =\pi /2`$ faster than the first one. In this light, the agreement between theory and experiment is remarkably good.

The structural similarities  between amorphous alloys and i–quasicrystals suggest that the quantum effect discussed above may be important in the latter systems as well. In fact, quasicrystals seem to fulfill all the necessary preconditions for this effect to occur, i.e. effectively diffusive electron motion  and $`\tau ^1\tau _{qp}^1`$. The latter is supported by the Fermi surface matching, i.e. by the experimental observation  and theoretical prediction  of structure–induced pseudogaps. Moreover, another more commonly known effect of disorder–enhanced Coulomb interaction, the $`\sqrt{|E\epsilon _F|}`$ behavior of the DOS in the pseudogap , may have been already observed in i–quasicrystals by tunneling measurements of the DOS . It is proposed to include the enhanced Friedel potential calculated in the present work in the pseudopotential of more quantitative ab initio calculations.

Numerous discussions with A. G. Aronov, P. Häussler, A. Huck, T. Kopp, Ch. Lauinger, and P. Wölfle are gratefully acknowledged. This work is supported by DFG through SP Quasikristalle.