The calculation of excited state properties with quantum Monte Carlo

D. M. Ceperley, B. Bernu

Research output: Contribution to journalArticlepeer-review

Abstract

A new Monte Carlo method for computing excited state properties of quantum systems is introduced. It is a generalization of the transient estimate method used for fermion Green's function Monte Carlo and of subspace projection methods used for computing eigenstates of matrices. The time dependent autocorrelation function of a vector of trial functions is calculated for a random walk generated by the imaginary-time Schrödinger equation and estimates of energy levels are determined by the eigenvalues of the matrix of correlation functions. This method is especially useful for treating states with the same symmetry as it automatically keeps higher states orthogonal to lower states. The estimated energy converges to the exact eigenvalue with a rate which decreases with increasing excitation energy, thus limiting the method to relatively low-lying states. The method is zero variance in the sense that as better trial functions are introduced, the statistical error decreases to zero. The method has a nontrivial bias which is analyzed. As an illustration, the eigenvalues of a double well are computed.

Original languageEnglish (US)
Pages (from-to)6316-6328
Number of pages13
JournalThe Journal of Chemical Physics
Volume89
Issue number10
DOIs
StatePublished - Jan 1 1988

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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