Direct non-Born-Oppenheimer variational calculations of all bound vibrational states corresponding to the first rotational excitation of D{sub 2} performed with explicitly correlated all-particle Gaussian functions

Journal Article · Thu May 07 04:00:00 EDT 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4919417· OSTI ID:22415743

Sharkey, Keeper L. ^[1]; Kirnosov, Nikita ^[2]; Adamowicz, Ludwik ^[1]

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1. Department of Chemistry and Biochemistry, University of Arizona, Tucson, Arizona 85721 (United States)
2. Department of Physics, University of Arizona, Tucson, Arizona 85721 (United States)

Direct variational calculations where the Born-Oppenheimer approximation is not assumed are done for all rovibrational states of the D{sub 2} molecule corresponding to first excited rotational level (the N = 1 states). All-particle explicitly correlated Gaussian basis functions are used in the calculations. The exponential parameters of the Gaussians are optimized with the aid of analytically calculated energy gradient determined with respect to these parameters. The results allow to determine the ortho-para spin isomerization energies as a function of the vibrational quantum number.

• OSTI ID: 22415743
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 17 Vol. 142; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
BASES
BORN-OPPENHEIMER APPROXIMATION
EXCITATION
GAUSS FUNCTION
ISOMERIZATION
MOLECULES
ROTATIONAL STATES
SPIN
VARIATIONAL METHODS
VIBRATIONAL STATES