INTERMOLECULAR BENDING LEVELS AND INFRARED SPECTROSCOPY OF OPEN-SHELL DIATOM-DIATOM COMPLEXES

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2001

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Ohio State University

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Abstract

A theoretical framework has been developed to describe the bending levels associated with an intermolecular potential of moderate anisotropy between an open-shell diatom and a diatomic partner, such as $OH-CO$ or $OH-N_{2}$. The model explicitly allows for coupling between the electronic and spin angular momenta of the open-shell OH radical and the vibrational angular momentum arising from the intermolecular bending motions of the complex. Using a dipole-quadrupole interaction potential, energies, wave functions, and transition moments are calculated to reveal the intermolecular energy pattern and expected bending vibrational spectrum for a moderately anisotropic system. The predicted spectrum is compared to that experimentally observed for the $OH-N_{2}$ complex in the OH overtone region. Explicit consideration of the OH radical spin-orbit $(\hat{l} \cdot \hat{s})$ and spin-decoupling $(\hat{j} \cdot \hat{s})$ interactions indicates that the spin-orbit splitting in the complex can differ, significantly from that of the OH monomer.

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$^{a}$Permanant address: Department of Chemistry, Amherst College, Amherst, MA 01002-5000
Author Institution: University of Pennsylvania; Department of Chemistry, University of Pennsylvania

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