Ab initio potential energy and dipole moment surfaces, infrared spectra, and vibrational predissociation dynamics of the 35Cl−⋯H2/D2 complexes

Autor:	M. M. Szczȩśniak, Grzegorz Chałasiński, Jacek Kłos, T. A. Grinev, Evan J. Bieske, Alexei A. Buchachenko
Rok vydání:	2003
Předmět:	Chemistry Ab initio General Physics and Astronomy Potential energy Dipole symbols.namesake Coupled cluster Total angular momentum quantum number Ab initio quantum chemistry methods symbols Physical and Theoretical Chemistry Atomic physics van der Waals force Basis set
Zdroj:	The Journal of Chemical Physics. 119:12931-12945
ISSN:	1089-7690 0021-9606
Popis:	Three-dimensional potential energy and dipole moment surfaces of the Cl−–H2 system are calculated ab initio by means of a coupled cluster method with single and double excitations and noniterative correction to triple excitations with augmented correlation consistent quadruple-zeta basis set supplemented with bond functions, and represented in analytical forms. Variational calculations of the energy levels up to the total angular momentum J=25 provide accurate estimations of the measured rotational spectroscopic constants of the ground van der Waals levels n=0 of the Cl−⋯H2/D2 complexes although they underestimate the red shifts of the mid-infrared spectra with v=0→v=1 vibrational excitation of the monomer. They also attest to the accuracy of effective radial interaction potentials extracted previously from experimental data using the rotational RKR procedure. Vibrational predissociation of the Cl−⋯H2/D2(v=1) complexes is shown to follow near-resonant vibrational-to-rotational energy transfer mechanism so...
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::b4844acf2911b0fd8e39121745e0c763 https://doi.org/10.1063/1.1626620 Zobrazit plný text záznamu