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Title: Normal-ordered second-quantized Hamiltonian for molecular vibrations

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 V{sup 1−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.
Authors:
 [1] ;  [2] ;  [1]
  1. Department of Chemistry, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, Illinois 61801 (United States)
  2. (Japan)
Publication Date:
OSTI Identifier:
22415343
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 18; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
97 MATHEMATICAL METHODS AND COMPUTING; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; DISTURBANCES; EXCITATION; GROUND STATES; HAMILTONIANS; PERTURBATION THEORY; PHONONS; SELF-CONSISTENT FIELD