New ab initio potential surfaces and three-dimensional quantum dynamics for transition state spectroscopy in ozone photodissociation

Effects of the transition dipole moment function on the dynamics of ozone photodissociation: an exact 3D quantum mechanical study

“…In the former, the TDMF has been taken into account explicitly while in the latter, the TDMF is assumed to be constant. This comparison however, leads to a conclusion that the eect of TDMF is rather signi®cant, being contrary to the conclusion of Yamashita et al [17]. For instance, there is a large deviation between Ref.…”

“…Leforestier et al [5] calculated ab initio TDMF, and it has been taken into account explicitly in their dynamical calculation. Yamashita et al [17] noted that the TDMF has only a negligible eect on the autocorrelation function, but no detailed comparative results have been provided by them. In fact, the eects of the TDMF can be derived indirectly from a comparison of the two previous calculations on the same YMLL PES [5], the calculation of Leforestier et al [5] (see Fig.…”

“…All the dynamical calculations reported to date reproduced well the broad background peak of the absorption spectrum (or the initial fast decay of the autocorrelation function), however, only few of them [5±9,17] were successful in reproducing the weak structures of the absorption spectrum (or the recurrence peaks of the autocorrelation function) qualitatively [5,8,17] and near quantitatively [6,7,9]. Motivated by the excellent reproducibility of the SW PES [11] for the experimental autocorrelation function as manifested by Balakrishnan et al [6], we recently [7] further calculated revibrational state distributions using the SW PES.…”

“…It was assumed implicitly without clear veri®-cation in the most previous calculations that the transition dipole moment function (TDMF) is constant. Two theoretical studies [5,17] have concerned with the TDMF. Leforestier et al [5] calculated ab initio TDMF, and it has been taken into account explicitly in their dynamical calculation.…”

Photodissociation of ozone at 193 nm by high-resolution photofragment translational spectroscopy

“…There exists an extensive body of theoretical work on ozone, both ab initio calculations [15][16][17][18][19][20][21][22] and dynamical studies. [13][14][15][23][24][25][26][27][28] Owing to its electronic complexity (it is effectively a spin-paired biradical), ozone represents a serious challenge to Hartree-Fock methods.…”