Normal-ordered second-quantized Hamiltonian for molecular vibrations

So Hirata, Matthew R. Hermes

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Abstract

A normal-ordered second-quantized form of the Hamiltonian is derived for quantum dynamics in a bound potential energy surface expressed as a Taylor series in an arbitrary set of orthogonal, delocalized coordinates centered at an arbitrary geometry. The constant, first-, and second-order excitation amplitudes of this Hamiltonian are identified as the ground-state energy, gradients, and frequencies, respectively, of the size-extensive vibrational self-consistent field (XVSCF) method or the self-consistent phonon method. They display the well-defined size dependence of V1-n/2, where V is the volume and n is the number of coordinates associated with the amplitudes. It is used to rapidly derive the equations of XVSCF and vibrational many-body perturbation methods with the Møller-Plesset partitioning of the Hamiltonian.

Original languageEnglish (US)
Article number184111
JournalJournal of Chemical Physics
Volume141
Issue number18
DOIs
StatePublished - Nov 14 2014

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ASJC Scopus subject areas

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

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