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

Journal Article · Tue Apr 14 00:00:00 EDT 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4916952· OSTI ID:22415626

Schwenke, David W., E-mail: [e-mail] ^[1]

---

1. NASA Ames Research Center, Mail Stop 258-2, P.O. Box 1, Moffett Field, California 94035-0001 (United States)

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.

• OSTI ID: 22415626
• Journal Information: Journal of Chemical Physics, Vol. 142, Issue 14; Other Information: (c) 2015 U.S. Government; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

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