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2013-06-14

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Please use this identifier to cite or link to this item: https://hdl.handle.net/2445/51245

Classical line shapes based on analytical solutions of bimolecular trajectories in collision induced emission. II. Reactive collisions

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http://dx.doi.org/10.1063/1.4808107

Abstract

The classical theory of collision induced emission (CIE) from pairs of dissimilar rare gas atoms was developed in Paper I [D. Reguera and G. Birnbaum, J. Chem. Phys. 125, 184304 (2006)] from a knowledge of the straight line collision trajectory and the assumption that the magnitude of the dipole could be represented by an exponential function of the inter-nuclear distance. This theory is extended here to deal with other functional forms of the induced dipole as revealed by ab initio calculations. Accurate analytical expression for the CIE can be obtained by least square fitting of the ab initio values of the dipole as a function of inter-atomic separation using a sum of exponentials and then proceeding as in Paper I. However, we also show how the multi-exponential fit can be replaced by a simpler fit using only two analytic functions. Our analysis is applied to the polar molecules HF and HBr. Unlike the rare gas atoms considered previously, these atomic pairs form stable bound diatomic molecules. We show that, interestingly, the spectra of these reactive molecules are characterized by the presence of multiple peaks. We also discuss the CIE arising from half collisions in excited electronic states, which in principle could be probed in photo-dissociation experiments.

Subject

Col·lisions (Física), Gasos rars, Espectroscòpia, Electrodinàmica, Química física, Enllaços químics

Subject (English)

Collisions (Physics), Rare gases, Spectrum analysis, Electrodynamics, Physical and theoretical chemistry, Chemical bonds

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Articles publicats en revistes (Física de la Matèria Condensada)

Citation

REGUERA, D. (David), RAWLINGS, Philip K. and BIRNBAUM, George. Classical line shapes based on analytical solutions of bimolecular trajectories in collision induced emission. II. Reactive collisions. Journal of Chemical Physics. 2013. Vol. 138, num. 22, pags. 224109-1-224109-10. ISSN 0021-9606. [consulted: 16 of June of 2026]. Available at: https://hdl.handle.net/2445/51245

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