2D-Block Geminals: a non 1-orthogonal and non 0-seniority model with reduced computational complexity

TL;DR

This paper introduces a novel geminal wave function model that relaxes orthogonality constraints, reducing computational complexity while maintaining accuracy in electronic structure calculations.

Contribution

The authors propose a non 1-orthogonal, non 0-seniority geminal model with weaker orthogonality constraints, simplifying calculations without losing electron indistinguishability.

Findings

More accurate than strongly orthogonal geminal products

Significantly reduced computational effort

Proof of concept confirms effectiveness

Abstract

We present a new geminal product wave function ansatz where the geminals are not constrained to be strongly orthogonal nor to be of seniority zero. Instead, we introduce weaker orthogonality constraints between geminals which significantly lower the computational effort, without sacrificing the indistinguishability of the electrons. That is to say, the electron pairs corresponding to the geminals are not fully distinguishable, and their product has still to be antisymmetrized according to the Pauli principle to form a \textit{bona fide} electronic wave function.Our geometrical constraints translate into simple equations involving the traces of products of our geminal matrices. In the simplest non-trivial model, a set of solutions is given by block-diagonal matrices where each block is of size 2x2 and consists of either a Pauli matrix or a normalized diagonal matrix, multiplied by a complex parameter to be optimized. With this simplified ansatz for geminals, the number of terms in the calculation of the matrix elements of quantum observables is considerably reduced. A proof of principle is reported and confirms that the ansatz is more accurate than strongly orthogonal geminal products while remaining computationally affordable.