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Title: A unified derivation of Hamiltonian and optical transition matrix elements for open shell diatomic and polyatomic molecules using transformation tools of modern quantum mechanics

In this work, we systematically derive the matrix elements of the nuclear rotation operators for open shell diatomic and polyatomic molecules in a parity adapted Hund’s case (a) basis. Our expressions are valid for an arbitrary number of electrons and arbitrary electronic configurations. The common ad hoc sign changes of angular momentum operators are shown to be equivalent to a change in phase of basis functions. We show how to relate this basis to that required for scattering calculations. We also give the expressions for Einstein A coefficients for electric dipole, electric quadrupole, and magnetic dipole transitions.
Authors:
 [1]
  1. NASA Ames Research Center, Mail Stop 258-2, P.O. Box 1, Moffett Field, California 94035-0001 (United States)
Publication Date:
OSTI Identifier:
22415626
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 14; Other Information: (c) 2015 U.S. Government; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; ANGULAR MOMENTUM OPERATORS; E1-TRANSITIONS; ELECTRONIC STRUCTURE; ELECTRONS; HAMILTONIANS; M1-TRANSITIONS; MATRIX ELEMENTS; MOLECULES; PARITY; QUANTUM MECHANICS; ROTATION; SCATTERING; TRANSFORMATIONS