INTRAMOLECULAR ELECTRONIC COUPLING ENHANCED COLLISIONAL DEACTIVATION OF HIGHLY VIBRATIONALLY EXCITED MOLECULES

被引:53
作者
HARTLAND, GV [1 ]
QIN, D [1 ]
DAI, HL [1 ]
机构
[1] UNIV PENN,DEPT CHEM,PHILADELPHIA,PA 19104
关键词
D O I
10.1063/1.468971
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The collisional deactivation of highly vibrationally excited NO2 and CS2 by a variety of buffer gases has been examined by time-resolved Fourier transform IR emission spectroscopy. The results show that there is a dramatic increase in the average energy removed per collision for NO2 excited above ∼10 000 cm-1 and for CS2 above ∼26 000 cm-1. These energies correspond to the origins of the lowest excited à 2B2/B̃ 2B1 states of NO2 and the lowest excited R 3A2 state of CS2. Mixing between these excited electronic states with the ground electronic state enhances collisional relaxation by allowing the electronic transition dipole to contribute to collisional energy transfer. © 1995 American Institute of Physics.
引用
收藏
页码:8677 / 8680
页数:4
相关论文
共 26 条
[21]   INTERNAL ENERGY-DISTRIBUTIONS FROM NITROGEN-DIOXIDE FLUORESCENCE .2. COLLISIONAL ENERGY-TRANSFER FROM EXCITED NITROGEN-DIOXIDE [J].
PATTEN, KO ;
JOHNSTON, HS .
JOURNAL OF PHYSICAL CHEMISTRY, 1993, 97 (39) :9904-9915
[22]   INTRA INTER POLYAD MIXING AND BREAKING OF SYMMETRICAL-ANTISYMMETRIC SELECTION RULE IN THE VIBRATIONAL-SPECTRA OF CS2 MOLECULE [J].
PIQUE, JP ;
MANNERS, J ;
SITJA, G ;
JOYEUX, M .
JOURNAL OF CHEMICAL PHYSICS, 1992, 96 (09) :6495-6508
[23]   NEAR THRESHOLD CHANNEL SELECTIVE PHOTODISSOCIATION OF NO2 [J].
ROBRA, U ;
ZACHARIAS, H ;
WELGE, KH .
ZEITSCHRIFT FUR PHYSIK D-ATOMS MOLECULES AND CLUSTERS, 1990, 16 (03) :175-188
[24]   ENERGY TRANSFER IN NEAR-RESONANT MOLECULAR COLLISIONS DUE TO LONG-RANGE FORCES WITH APPLICATION TO TRANSFER OF VIBRATIONAL ENERGY FROM NU3 MODE OF CO2 TO N2 [J].
SHARMA, RD ;
BRAU, CA .
JOURNAL OF CHEMICAL PHYSICS, 1969, 50 (02) :924-&
[25]   NEAR-RESONANT VIBRATIONAL ENERGY TRANSFER IN N2-CO2 MIXTURES [J].
SHARMA, RD ;
BRAU, CA .
PHYSICAL REVIEW LETTERS, 1967, 19 (22) :1273-&
[26]   TIME-DEPENDENT THERMAL LENSING MEASUREMENTS OF V-T ENERGY-TRANSFER FROM HIGHLY EXCITED NO2 [J].
TOSELLI, BM ;
WALUNAS, TL ;
BARKER, JR .
JOURNAL OF CHEMICAL PHYSICS, 1990, 92 (08) :4793-4804