The dynamics of nonadiabatic transitions in collisions between the I 2(E) and I2(X) molecules

Yu V. Suleimanov, T. V. Shcherbul', A. A. Buchachenko

Research output: Contribution to journalArticlepeer-review

4 Citations (Scopus)

Abstract

The paper presents the results of a theoretical study of the dynamics of nonadiabatic transitions between the ion-pair states E0 g + and D0 u + of the I2 molecule induced by collisions with the I2 molecule in the ground electronic state X0 g + . The potential energy surfaces and diabatic coupling matrix elements of electronic states were obtained using a model based on the diatomics-in-molecule approximation. Special perturbation theory for intermolecular interaction was used to show that the large transition dipole moment between the E0 g + and D0 u + states caused the appearance of additional long-range corrections, an electrostatic dipole-quadrupole correction to the diabatic coupling matrix elements and induction dipole-dipole correction to the potential energy surface. The influence of these corrections on nonadiabatic dynamics was studied at the level of the semiclassical approximation. The electrostatic correction was found to sharply increase the contribution of resonance (accompanied by minimum kinetic energy changes) vibronic transitions at large distances between the colliding molecules. The induction correction had the opposite effect because of the high transition probability at short distances. The results obtained were in qualitative agreement with experimental data. The conclusion was drawn that obtaining quantitative agreement required a more balanced inclusion of interactions at short and long distances.

Original languageEnglish
Pages (from-to)58-68
Number of pages11
JournalRussian Journal of Physical Chemistry A
Volume81
Issue number1
DOIs
Publication statusPublished - Jan 2007
Externally publishedYes

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