Multideterminant wave functions in quantum Monte Carlo

Miguel A. Morales, Jeremy McMinis, Bryan K. Clark, Jeongnim Kim, Gustavo E. Scuseria

Research output: Contribution to journalReview article

Abstract

Quantum Monte Carlo (QMC) methods have received considerable attention over past decades due to their great promise for providing a direct solution to the many-body Schrodinger equation in electronic systems. Thanks to their low scaling with the number of particles, QMC methods present a compelling competitive alternative for the accurate study of large molecular systems and solid state calculations. In spite of such promise, the method has not permeated the quantum chemistry community broadly, mainly because of the fixed-node error, which can be large and whose control is difficult. In this Perspective, we present a systematic application of large scale multideterminant expansions in QMC and report on its impressive performance with first row dimers and the 55 molecules of the G1 test set. We demonstrate the potential of this strategy for systematically reducing the fixed-node error in the wave function and for achieving chemical accuracy in energy predictions. When compared to traditional quantum chemistry methods like MP2, CCSD(T), and various DFT approximations, the QMC results show a marked improvement over all of them. In fact, only the explicitly correlated CCSD(T) method with a large basis set produces more accurate results. Further developments in trial wave functions and algorithmic improvements appear promising for rendering QMC as the benchmark standard in large electronic systems.

Original languageEnglish (US)
Pages (from-to)2181-2188
Number of pages8
JournalJournal of Chemical Theory and Computation
Volume8
Issue number7
DOIs
StatePublished - Jul 10 2012

ASJC Scopus subject areas

  • Computer Science Applications
  • Physical and Theoretical Chemistry

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