Premium
Variational treatment of the vibrational Hamiltonian for NH 3 and H 2 NO
Author(s) -
Marsal Philippe,
Roche Michel
Publication year - 2002
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.10033
Subject(s) - anharmonicity , hamiltonian (control theory) , inversion (geology) , vibration , physics , chemistry , computational chemistry , mathematics , quantum mechanics , mathematical optimization , paleontology , structural basin , biology
Abstract The full vibrational Hamiltonian for the inversion of NH 3 and H 2 NO has been diagonalized in a basis set that is the direct product of functions of the inversion coordinate and of harmonic vibrational functions independent of this inversion coordinate. The kinetic part of the Hamiltonian matrix is constructed with the use of the closure relation for these vibrational functions. The method is tested with the potential function which is supposed to be harmonic for the vibrations orthogonal to the inversion coordinate: the first computed levels are in good agreement with experimental levels for NH 3 . For higher levels, anharmonic terms should be included. © 2002 Wiley Periodicals, Inc. J Comput Chem 23: 541–547, 2002; DOI 10.1002/jcc.10033