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Unbiased reduced density matrices and electronic properties from full configuration interaction quantum Monte Carlo.

Accepted version
Peer-reviewed

Type

Article

Change log

Authors

Overy, Catherine 
Booth, George H 
Blunt, NS 
Shepherd, James J 
Cleland, Deidre 

Abstract

Properties that are necessarily formulated within pure (symmetric) expectation values are difficult to calculate for projector quantum Monte Carlo approaches, but are critical in order to compute many of the important observable properties of electronic systems. Here, we investigate an approach for the sampling of unbiased reduced density matrices within the full configuration interaction quantum Monte Carlo dynamic, which requires only small computational overheads. This is achieved via an independent replica population of walkers in the dynamic, sampled alongside the original population. The resulting reduced density matrices are free from systematic error (beyond those present via constraints on the dynamic itself) and can be used to compute a variety of expectation values and properties, with rapid convergence to an exact limit. A quasi-variational energy estimate derived from these density matrices is proposed as an accurate alternative to the projected estimator for multiconfigurational wavefunctions, while its variational property could potentially lend itself to accurate extrapolation approaches in larger systems.

Description

Keywords

0105 Mathematical Physics

Journal Title

J Chem Phys

Conference Name

Journal ISSN

0021-9606
1089-7690

Volume Title

141

Publisher

AIP Publishing
Sponsorship
Engineering and Physical Sciences Research Council (EP/J003867/1)