Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 117, Issue 11, Pages 5221-5233Publisher
AMER INST PHYSICS
DOI: 10.1063/1.1499720
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To explore the role of molecular structure in collisions that relax highly excited polyatomic molecules, we have studied collisional deactivation of a series of highly vibrationally excited methylated pyridines (E(vib)similar to38 500 cm(-1)) in a CO(2) bath. Complementary studies that investigated quenching by H(2)O have been presented in Part I of this series [M. S. Elioff, M. Fang, and A. S. Mullin, J. Chem. Phys. 115, 6990 (2001)]. We have used high-resolution transient infrared absorption probing to measure rotational and translational energy gain in individual quantum levels of CO(2) (00(0)0) that are populated via collisions with vibrationally excited picoline (2-methylpyridine) and lutidine (2,6-dimethylpyridine). Vibrationally excited picoline and lutidine were prepared by absorption of pulsed lambda=266 nm light and fast internal decay to the ground electronic state. The nascent distribution of CO(2) (00(0)0) rotational states was measured for J=60-78. Translational energy gain distributions were determined for the J=60-80 states of CO(2) (00(0)0) using Doppler-broadened linewidth measurements. Energy transfer probabilities were determined by measuring absolute energy transfer rate constants for energy gain into specific CO(2) quantum states. These results are compared to previous single-collision energy transfer studies on hot pyridine [M. C. Wall, B. Stewart, and A. S. Mullin, J. Chem. Phys. 108, 9658 (1998)] and hot pyrazine [M. C. Wall and A. S. Mullin, J. Chem. Phys. 108, 9658 (1998)] initially excited with 266 nm light and quenched via collisions with CO(2). We find that donor methylation reduces the amount of translational and rotational energy imparted to the CO(2) (00(0)0) high-J states, but that the cross section for exciting the high-J states of CO(2) (00(0)0) increases upon donor methylation. Fermi's golden rule is used to describe the relaxation process, and the energy transfer distribution functions for DeltaE>4000 cm(-1) are found to correlate remarkably well to the energy dependence of the density of states of the hot donor molecule. This analysis is also successfully applied to earlier quenching data for vibrationally excited C(6)F(6) [C. A. Michaels , J. Chem. Phys. 106, 7055 (1997)], suggesting that this may be a general approach for describing relaxation of highly excited molecules. (C) 2002 American Institute of Physics.
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