Multiconfiguration time-dependent Hartree-Fock treatment of electronic and nuclear dynamics in diatomic molecules

Journal Article · Wed Jun 15 04:00:00 EDT 2011 · Physical Review. A

DOI:https://doi.org/10.1103/PHYSREVA.83.063416· OSTI ID:21550139

Haxton, D J; Lawler, K V ^[1]; McCurdy, C W ^[1]

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1. Chemical Sciences and Ultrafast X-ray Science Laboratory, Lawrence Berkeley National Laboratory, Berkeley, California, 94720 (United States)

The multiconfiguration time-dependent Hartree-Fock (MCTDHF) method is formulated for treating the coupled electronic and nuclear dynamics of diatomic molecules without the Born-Oppenheimer approximation. The method treats the full dimensionality of the electronic motion, uses no model interactions, and is in principle capable of an exact nonrelativistic description of diatomics in electromagnetic fields. An expansion of the wave function in terms of configurations of orbitals whose dependence on internuclear distance is only that provided by the underlying prolate spheroidal coordinate system is demonstrated to provide the key simplifications of the working equations that allow their practical solution. Photoionization cross sections are also computed from the MCTDHF wave function in calculations using short pulses.

• OSTI ID: 21550139
• Journal Information: Physical Review. A, Journal Name: Physical Review. A Journal Issue: 6 Vol. 83; ISSN 1050-2947; ISSN PLRAAN
• Country of Publication: United States
• Language: English

Related Subjects

71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
74 ATOMIC AND MOLECULAR PHYSICS
APPROXIMATIONS
BORN-OPPENHEIMER APPROXIMATION
CALCULATION METHODS
CONFIGURATION
CROSS SECTIONS
ELECTROMAGNETIC FIELDS
FUNCTIONS
HARTREE-FOCK METHOD
INTERACTIONS
IONIZATION
MATHEMATICAL SOLUTIONS
MOLECULES
PHOTOIONIZATION
PULSES
SPHERICAL CONFIGURATION
TIME DEPENDENCE
WAVE FUNCTIONS