Ground-state wavefunction of macroscopic electron systems

TL;DR

This paper introduces a novel approach to resolve the exponential wall problem in large electron systems by reformulating wavefunctions in Liouville space using cumulants, enabling accurate ground-state calculations for solids.

Contribution

It presents a method to transform multiplicative wavefunctions into additive operators in Liouville space, improving electronic structure calculations for macroscopic systems.

Findings

The approach avoids the exponential growth in Hilbert space dimensions.

The method has been successfully applied to ground-state calculations of solids.

Matrix product states are integrated into the formalism, enhancing one-dimensional system analysis.

Abstract

Wavefunctions for large electron numbers $N$ are plagued by the Exponential Wall Problem (EWP), i.e., an exponential increase in the dimensions of Hilbert space with $N$. Therefore they loose their meaning for macroscopic systems, a point stressed in particular by W. Kohn. The EWP has to be resolved in order to be able to perform electronic structure calculations, e.g., for solids. The origin of the EWP is the multiplicative property of wavefunctions when independent subsystems are considered. Therefore it can only be avoided when wavefunctions are formulated so that they are additive instead, in particular when matrix elements involving them are calculated. We describe how this is done for the ground state of a macroscopic electron system. Going over from a multiplicative to an additive quantity requires taking a logarithm. Here it implies going over from Hilbert space to the operator- or Liouville space with a metric based on cumulants. The operators which define the ground-state wavefunction generate fluctuations from a mean-field state. The latter does not suffer from an EWP and therefore may serve as a vacuum state. The fluctuations have to be {\it connected} like the ones caused by pair interactions in a classical gas when the free energy is calculated (Meyer's cluster expansion). This fixes the metric in Liouville space. The scheme presented here provides a solid basis for electronic structure calculations for the ground state of solids. In fact, its applicability has already been proven. We discuss also matrix product states, which have been applied to one-dimensional systems with results of high precision. Although these states are formulated in Hilbert space they are processed by using operators in Liouville space. We show that they fit into the general formalism described above.