Electric transition dipole moment in pre-Born-Oppenheimer molecular structure theory

Benjamin Simmen, Edit Mátyus, Markus Reiher

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This paper presents the calculation of the electric transition dipole moment in a pre-Born-Oppenheimer framework. Electrons and nuclei are treated equally in terms of the parametrization of the non-relativistic total wave function, which is written as a linear combination of basis functions constructed from explicitly correlated Gaussian functions and the global vector representation. The integrals of the electric transition dipole moment are derived corresponding to these basis functions in both the length and the velocity representation. The calculations are performed in laboratory-fixed Cartesian coordinates without relying on coordinates which separate the center of mass from the translationally invariant degrees of freedom. The effect of the overall motion is eliminated through translationally invariant integral expressions. The electric transition dipole moment is calculated between two rovibronic levels of the H2 molecule assignable to the lowest rovibrational states of the X 1Σg+ B 1Σu+ electronic states in the clamped-nuclei framework. This is the first evaluation of this quantity in a full quantum mechanical treatment without relying on the Born-Oppenheimer approximation.

Original languageEnglish
Article number154105
JournalJournal of Chemical Physics
Issue number15
Publication statusPublished - Oct 21 2014


ASJC Scopus subject areas

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

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