Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 110, Issue 9, Pages 3266-3272Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp054762y
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Strong collisions of highly vibrationally excited picoline isomers and CO2 (00(0)0) were investigated using high resolution transient IR absorption probing to investigate the role of donor state density. Vibrationally excited 3-picoline and 4-picoline (3-methylpyridine and 4 methylpyridine) with E-vib = 38300 cm(-1) were prepared by 266 nm excitation followed by rapid internal conversion. Transient IR probe measurements of the nascent rotational and translational energy gain in CO2 (00(0)0) show that large Delta E collisions for 3- and 4-picoline are similar to those for excited 2-picoline. The probability distributions for the large Delta E energy transfer of the three isomers have similar dependence on Delta E. The results are compared with other earlier results demonstrating that the shape of the large Delta E probability distribution correlates with the Delta E dependence of the donor vibrational state density. The results are discussed in terms of the GRETCHEN model for collisional relaxation.
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