Accurate non-Born-Oppenheimer calculations of the complete pure vibrational spectrum of D2 with including relativistic corrections

Sergiy Bubin, Monika Stanke, Ludwik Adamowicz

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

In this work we report very accurate variational calculations of the complete pure vibrational spectrum of the D2 molecule performed within the framework where the Born-Oppenheimer (BO) approximation is not assumed. After the elimination of the center-of-mass motion, D2 becomes a three-particle problem in this framework. As the considered states correspond to the zero total angular momentum, their wave functions are expanded in terms of all-particle, one-center, spherically symmetric explicitly correlated Gaussian functions multiplied by even non-negative powers of the internuclear distance. The nonrelativistic energies of the states obtained in the non-BO calculations are corrected for the relativistic effects of the order of 2 (where 1c is the fine structure constant) calculated as expectation values of the operators representing these effects.

Original languageEnglish
Article number074110
JournalJournal of Chemical Physics
Volume135
Issue number7
DOIs
Publication statusPublished - Aug 21 2011
Externally publishedYes

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Vibrational spectra
vibrational spectra
Born approximation
Born-Oppenheimer approximation
Angular momentum
relativistic effects
Wave functions
center of mass
elimination
angular momentum
fine structure
wave functions
operators
Molecules
molecules
energy

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Accurate non-Born-Oppenheimer calculations of the complete pure vibrational spectrum of D2 with including relativistic corrections. / Bubin, Sergiy; Stanke, Monika; Adamowicz, Ludwik.

In: Journal of Chemical Physics, Vol. 135, No. 7, 074110, 21.08.2011.

Research output: Contribution to journalArticle

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