Correlated sampling of Monte Carlo derivatives with iterative-fixed sampling

Journal Article · Sun Nov 15 00:00:00 EST 1992 · Journal of Chemical Physics; (United States)

DOI:https://doi.org/10.1063/1.463478· OSTI ID:7156623

Sun, Z; Lester, Jr, W A ^[1]; Hammond, B L ^[2]

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1. Chemical Sciences Division, Lawrence Berkeley Laboratory and Department of Chemistry, University of California at Berkeley, Berkeley, California 94720 (United States)
2. Fujitsu America, Inc., Computational Research Division, San Jose, California 95134-2022 (United States)

A correlated sampling method for determining the energy and other property derivatives by finite difference is implemented within variational Monte Carlo. Determination of derivatives takes place over a fixed sample of electronic coordinates, so it is possible to distinguish small energy or other property differences accurately. Using finite differences avoids the evaluation of complicated derivative expressions and can be applied directly to Green's function Monte Carlo methods without the need for derivatives of the Green's function. The algorithm can be used to evaluate derivatives with respect to any parameters in the Hamiltonian or in the trial function. In this paper, it is applied to H{sub 2} and Li{sub 2} for their energy derivatives with respect to nuclear coordinates. Results are in agreement with experimental data.

• DOE Contract Number: AC03-76SF00098
• OSTI ID: 7156623
• Journal Information: Journal of Chemical Physics; (United States), Vol. 97:10; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
HYDROGEN
HAMILTONIANS
LITHIUM
ALGORITHMS
CALCULATION METHODS
COORDINATES
ELECTRONIC STRUCTURE
FINITE DIFFERENCE METHOD
GREEN FUNCTION
ITERATIVE METHODS
MOLECULES
MONTE CARLO METHOD
QUANTUM MECHANICS
USES
VARIATIONAL METHODS
ALKALI METALS
ELEMENTS
FUNCTIONS
MATHEMATICAL LOGIC
MATHEMATICAL OPERATORS
MECHANICS
METALS
NONMETALS
NUMERICAL SOLUTION
QUANTUM OPERATORS
664100* - Theory of Electronic Structure of Atoms & Molecules- (1992-)