Size-extensive vibrational self-consistent field methods with anharmonic geometry corrections

Matthew R. Hermes, Murat Keeli, So Hirata

Research output: Contribution to journalArticlepeer-review

Abstract

In the size-extensive vibrational self-consistent field (XVSCF) method introduced earlier [M. Keeli and S. Hirata, J. Chem. Phys. 135, 134108 (2011)]10.1063/1.3644895, only a small subset of even-order force constants that can form connected diagrams were used to compute extensive total energies and intensive transition frequencies. The mean-field potentials of XVSCF formed with these force constants have been shown to be effectively harmonic, making basis functions, quadrature, or matrix diagonalization in the conventional VSCF method unnecessary. We introduce two size-consistent VSCF methods, XVSCF(n) and XVSCF[n], for vibrationally averaged geometries in addition to energies and frequencies including anharmonic effects caused by up to the nth-order force constants. The methods are based on our observations that a small number of odd-order force constants of certain types can form open, connected diagrams isomorphic to the diagram of the mean-field potential gradients and that these nonzero gradients shift the potential minima by intensive amounts, which are interpreted as anharmonic geometry corrections. XVSCF(n) evaluates these mean-field gradients and force constants at the equilibrium geometry and estimates this shift accurately, but approximately, neglecting the coupling between these two quantities. XVSCF[n] solves the coupled equations for geometry corrections and frequencies with an iterative algorithm, giving results that should be identical to those of VSCF when applied to an infinite system. We present the diagrammatic and algebraic definitions, algorithms, and initial implementations as well as numerical results of these two methods. The results show that XVSCF(n) and XVSCF[n] reproduce the vibrationally averaged geometries of VSCF for naphthalene and anthracene in their ground and excited vibrational states accurately at fractions of the computational cost.

Original languageEnglish (US)
Article number234109
JournalJournal of Chemical Physics
Volume136
Issue number23
DOIs
StatePublished - Jun 21 2012

ASJC Scopus subject areas

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

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