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Relativistic E×T Jahn–Teller effect in tetrahedral systems
It is shown that 2E states in tetrahedral systems exhibit a linear E×T Jahn–Teller effect which is of purely relativistic origin (that is, it arises from the spin-orbit-coupling operator)....

Energy derivatives in quantum Monte Carlo involving the zero-variance property

J. Chem. Phys. 129, 224101 (2008); doi:10.1063/1.3013817

Published 8 December 2008

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A. Badinski, J. R. Trail, and R. J. Needs
Theory of Condensed Matter Group, Cavendish Laboratory, J. J. Thomson Avenue, Cambridge CB3 0HE, United Kingdom
We give an exact expression for the nth derivative of the expectation value of the energy that satisfies the zero-variance (ZV) principle when the wave function and its first n derivatives are exact. The ZV principle was previously applied to the first energy derivative (“force”) within the variational Monte Carlo and mixed-estimator diffusion Monte Carlo methods. We present a new expression for the force in pure-estimator diffusion Monte Carlo that satisfies the ZV principle and can be evaluated much more efficiently than previous expressions while maintaining comparable accuracy. This expression is the sum of a pure expectation value and a variational expectation value, which separately satisfy the ZV principle. The bias in this force estimator is second order in the deviation of the trial wave function from the diffusion Monte Carlo wave function. Results for small molecules demonstrate the accuracy of the method and its statistical efficiency. ©2008 American Institute of Physics
History: Received 7 August 2008; accepted 16 October 2008; published 8 December 2008
Permalink: http://link.aip.org/link/?JCPSA6/129/224101/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.15.xt
    Variational techniques in atomic and molecular physics
  • 33.15.Dj
    Interatomic distances and angles in molecules
  • 33.15.Mt
    Molecular rotation, vibration, and vibration-rotation constants
  • 33.20.Tp
    Vibrational analysis (molecular spectra)
  • 33.15.Bh
    General molecular conformation and symmetry; stereochemistry
  • YEAR: 2008

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ISSN:
0021-9606 (print)   1089-7690 (online)
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REFERENCES (30)
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