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Title: 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

Abstract

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.

Authors:
 [1];  [2];  [1];  [3]
  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)
  3. (United States)
Publication Date:
OSTI Identifier:
22415743
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 142; Journal Issue: 17; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; BASES; BORN-OPPENHEIMER APPROXIMATION; EXCITATION; GAUSS FUNCTION; ISOMERIZATION; MOLECULES; ROTATIONAL STATES; SPIN; VARIATIONAL METHODS; VIBRATIONAL STATES

Citation Formats

Sharkey, Keeper L., Kirnosov, Nikita, Adamowicz, Ludwik, E-mail: ludwik@u.arizona.edu, and Department of Physics, University of Arizona, Tucson, Arizona 85721. 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. United States: N. p., 2015. Web. doi:10.1063/1.4919417.
Sharkey, Keeper L., Kirnosov, Nikita, Adamowicz, Ludwik, E-mail: ludwik@u.arizona.edu, & Department of Physics, University of Arizona, Tucson, Arizona 85721. 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. United States. doi:10.1063/1.4919417.
Sharkey, Keeper L., Kirnosov, Nikita, Adamowicz, Ludwik, E-mail: ludwik@u.arizona.edu, and Department of Physics, University of Arizona, Tucson, Arizona 85721. Thu . "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". United States. doi:10.1063/1.4919417.
@article{osti_22415743,
title = {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},
author = {Sharkey, Keeper L. and Kirnosov, Nikita and Adamowicz, Ludwik, E-mail: ludwik@u.arizona.edu and Department of Physics, University of Arizona, Tucson, Arizona 85721},
abstractNote = {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.},
doi = {10.1063/1.4919417},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 17,
volume = 142,
place = {United States},
year = {2015},
month = {5}
}