Non-adiabatic mass correction to the rovibrational states of molecules: Numerical application for the H 2 + molecular ion

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Abstract

General transformation expressions of the second-order non-adiabatic Hamiltonian of the atomic nuclei, including the kinetic-energy correction terms, are derived upon the change from laboratory-fixed Cartesian coordinates to general curvilinear coordinate systems commonly used in rovibrational computations. The kinetic-energy or so-called "mass-correction" tensor elements are computed with the stochastic variational method and floating explicitly correlated Gaussian functions for the H2+ molecular ion in its ground electronic state. {Further numerical applications for the 4He2+ molecular ion are presented in the forthcoming paper, Paper II [E. Mátyus, J. Chem. Phys. 149, 194112 (2018)]}. The general, curvilinear non-adiabatic kinetic energy operator expressions are used in the examples, and non-adiabatic rovibrational energies and corrections are determined by solving the rovibrational Schrödinger equation including the diagonal Born-Oppenheimer as well as the mass-tensor corrections.

Original languageEnglish
Article number194111
JournalJournal of Chemical Physics
Volume149
Issue number19
DOIs
Publication statusPublished - Nov 21 2018

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molecular ions
Kinetic energy
Ions
Molecules
Tensors
kinetic energy
molecules
Hamiltonians
Electronic states
tensors
Cartesian coordinates
spherical coordinates
floating
operators
nuclei
electronics
energy

ASJC Scopus subject areas

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

Cite this

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abstract = "General transformation expressions of the second-order non-adiabatic Hamiltonian of the atomic nuclei, including the kinetic-energy correction terms, are derived upon the change from laboratory-fixed Cartesian coordinates to general curvilinear coordinate systems commonly used in rovibrational computations. The kinetic-energy or so-called {"}mass-correction{"} tensor elements are computed with the stochastic variational method and floating explicitly correlated Gaussian functions for the H2+ molecular ion in its ground electronic state. {Further numerical applications for the 4He2+ molecular ion are presented in the forthcoming paper, Paper II [E. M{\'a}tyus, J. Chem. Phys. 149, 194112 (2018)]}. The general, curvilinear non-adiabatic kinetic energy operator expressions are used in the examples, and non-adiabatic rovibrational energies and corrections are determined by solving the rovibrational Schr{\"o}dinger equation including the diagonal Born-Oppenheimer as well as the mass-tensor corrections.",
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