MOLECULAR DYNAMICS SIMULATION OF THE $^{3}\Pi_{g}$ (ION-PAIR) $\rightarrow ^{3}\Pi_{u}$ (VALENCE) RED-SHIFTED TRANSITIONS OF $Cl_{2}$ IN NEON MATRICES
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Date
1998
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Publisher
Ohio State University
Abstract
The features of the emission bands corresponding to the transition from the ion-pair $^{3}\Pi_{g}$ state to the valence $^{3}\Pi_{u}$ state of $Cl_{2}$ in neon matrices have been modelled by the molecular dynamics simulations with the diatomics-in-molecules (DIM) interaction $potentials^{a,b}$. The experimental potential curves of $Cl_{2}$ in the gas phase have been employed for initial numerical calculations of the $^{3}\Pi_{g}(v^{\prime})\to^{3}\Pi_{u}(v^{\prime \prime})$ band positions and the corresponding Franck-Condon factors. The matrix-perturbed potential curves of the trapped $Cl_{2}$ molecule have been evaluated by the direct calculation of the corresponding cuts through the $Cl_{2}@Ne_{n}$ multi-dimentional potential energy surface constructed with the DIM techniques. The parameters of the model have been verified at the preliminary stage on the three-atomic van der Waals complex $Ne\ldots Cl_{2}$. The results of simulations show a remarkable coincidence with the experimental findings of Guertler, Kunz and Le Calve [J.Chem.Phys. 91 (1989) 6020], namely, the matrix environment causes the quantitatively reproduced red shifts in the$ (0, v^{\prime \prime})$ band positions as well as the noticeable changes in band intensities.
Description
$^{a}$ B.L. Grigorenko, A.V. Nemukhin, A.A. Buchachenko, N.F. Stepanov, and S. Ya. Umanskii, J.Chem.Phys. 106, 4575 (1997). $^{b}$ B.L. Grigorenko, A.V. Nemukhin, and V.A. Apkarian, Chem.Phys. 219, 161 (1997).
Author Institution: Department of Chemistry, Moscow State University
Author Institution: Department of Chemistry, Moscow State University