A global electric dipole function of ammonia and isotopomers in the electronic ground state - Archive ouverte HAL
Article Dans Une Revue The Journal of Chemical Physics Année : 2003

A global electric dipole function of ammonia and isotopomers in the electronic ground state

R. Marquardt
M. Quack
  • Fonction : Auteur
I. Thanopulos
  • Fonction : Auteur
D. Luckhaus
  • Fonction : Auteur

Résumé

A global analytical representation of the electric dipole hypersurface for ammonia and isotopomers is developed as a function of bond lengths and bond angles. Its simple and general form allows for the simultaneous description of all three dipole moment components using a small number of parameters. The parameter values are determined by adjustment to dipole moment values obtained from ab initio calculations at the second-order Moller-Plesset and multiconfiguration self-consistent field level of theory. The dipole function is used to calculate six-dimensional transition moments for NH3, using wave functions obtained from a variational calculation and a global analytical representation of the potential hypersurface. The comparison with experiment demonstrates a fairly reliable description of the electric dipole hypersurface for molecular structures with potential energy equivalent to up to 10000 cm(-1). At higher excitations a qualitatively correct asymptotic behavior of the dipole function is assured by construction. (C) 2003 American Institute of Physics.
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Dates et versions

hal-00693482 , version 1 (02-05-2012)

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Citer

R. Marquardt, M. Quack, I. Thanopulos, D. Luckhaus. A global electric dipole function of ammonia and isotopomers in the electronic ground state. The Journal of Chemical Physics, 2003, 119 (20), pp.10724--10732. ⟨10.1063/1.1617272⟩. ⟨hal-00693482⟩
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