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An excited-state approach within full configuration interaction quantum Monte Carlo.


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Authors

Blunt, NS 
Smart, Simon D 
Booth, George H 

Abstract

We present a new approach to calculate excited states with the full configuration interaction quantum Monte Carlo (FCIQMC) method. The approach uses a Gram-Schmidt procedure, instantaneously applied to the stochastically evolving distributions of walkers, to orthogonalize higher energy states against lower energy ones. It can thus be used to study several of the lowest-energy states of a system within the same symmetry. This additional step is particularly simple and computationally inexpensive, requiring only a small change to the underlying FCIQMC algorithm. No trial wave functions or partitioning of the space is needed. The approach should allow excited states to be studied for systems similar to those accessible to the ground-state method due to a comparable computational cost. As a first application, we consider the carbon dimer in basis sets up to quadruple-zeta quality and compare to existing results where available.

Description

Keywords

Algorithms, Monte Carlo Method, Quantum Theory

Journal Title

J Chem Phys

Conference Name

Journal ISSN

0021-9606
1089-7690

Volume Title

143

Publisher

AIP Publishing
Sponsorship
Engineering and Physical Sciences Research Council (EP/J003867/1)
N.S.B. gratefully acknowledges Trinity College, Cambridge for funding. G.H.B. gratefully acknowledges the Royal Society for funding via a university research fellowship. This work has been supported by the EPSRC under grant no. EP/J003867/1.