Vibrational predissociation of ArH2O

Abstract

Accurate close-coupling calculations are used to investigate the vibrational predissociation of ArH 2 0 as a function of the overall rotation J of the van der Waals complex. A full vibrational and rotational basis of H 2 0 states is used in the calculation. The potential energy surface is of a form due to Cohen and Saykally and derived from far-infrared spectra, with an additional term to introduce the dependence on the vibrations of H 2 0. The linewidths calculated in this work show a maximum at J = 6 and it is found that Fermi resonances affect dramatically the magnitude of the calculated linewidths. Good agreement with experimentally measured linewidths of Nesbitt and Lascola is achieved and the calculations provide a simple picture for the J dependence of the linewidths.

Vibrational predissociation dynamics of methane–Ar: an ab initio approach

“…), q 1 , q 3 , Let us Ðrst consider the normal modes and substitute into eqn. (4) Upon noticing POE \ (134). that and we Ðnd…”

Experimental and theoretical investigations of H2O–Ar

“…[2][3][4] H 2 O-RG complexes, in particular, attracted attention in both early and recent literature. 5 Microwave (MW) and farinfrared (FIR) investigations, [6][7][8][9][10][11][12][13][14][15][16][17] together with ab initio and other theoretical studies, [18][19][20][21][22][23][24][25][26][27][28][29] and more 30 provided extended information. Some of this selected literature input combines experimental and theoretical methods.…”

Photodissociation of the methane–argon complex. I. Ab initio intermolecular potential depending on the methane vibrational coordinates

“…When one neglects the intramonomer vibrations and their coupling with intermolecular vibrations, one loses sight of some interesting phenomena, to mention a few: red 3 and blue 4 shifts of XuH stretching vibrations upon hydrogen bonding XuH¯Y and line broadenings due to vibrational predissociation. [5][6][7][8][9] It is therefore not surprising that much recent research in the field of intermolecular forces is aimed at obtaining full three-dimensional potential energy surfaces ͑PESs͒ for atom-diatom complexes [10][11][12][13][14][15][16] and the inclusion of relevant intramonomer degrees of freedom [17][18][19] for polyatomic monomers. When a PES is described by an atomatom model, the coupling between inter-and intramolecular vibrations is implicitly included by letting the force centers vibrate with the atoms.…”