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Title: Leading order nonadiabatic corrections to rovibrational levels of H{sub 2}, D{sub 2}, and T{sub 2}

An efficient computational approach to nonadiabatic effects in the hydrogen molecule (H{sub 2}, D{sub 2}, and T{sub 2}) is presented. The electronic wave function is expanded in the James-Coolidge basis set, which enables obtaining a very high accuracy of nonadiabatic potentials. A single point convergence of the potentials with growing size of the basis set reveals a relative accuracy ranging from 10{sup −8} to 10{sup −13}. An estimated accuracy of the leading nonadiabatic correction to the rovibrational energy levels is of the order of 10{sup −7} cm{sup −1}. After a significant increase in the accuracy of the Born-Oppenheimer and adiabatic calculations, the nonadiabatic results presented in this report constitute another step towards highly accurate theoretical description of the hydrogen molecule.
Authors:
 [1] ;  [2]
  1. Faculty of Physics, University of Warsaw, Pasteura 5, 02-093 Warsaw (Poland)
  2. Faculty of Chemistry, Adam Mickiewicz University, Umultowska 89b, 61-614 Poznań (Poland)
Publication Date:
OSTI Identifier:
22489726
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 143; Journal Issue: 3; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACCURACY; BORN-OPPENHEIMER APPROXIMATION; CONVERGENCE; CORRECTIONS; ENERGY LEVELS; HYDROGEN; MOLECULES; POTENTIALS; WAVE FUNCTIONS