EFFICIENT COLLISIONAL ENERGY-TRANSFER OF VIBRATIONALLY HIGHLY EXCITED C6F6 MOLECULES IN THE GROUND ELECTRONIC STATE

被引:44
作者
DAMM, M
HIPPLER, H
OLSCHEWSKI, HA
TROE, J
WILLNER, J
机构
[1] Institut für Physikalische Chemie, Universität Göttingen, Tammannstrasse 6
来源
ZEITSCHRIFT FUR PHYSIKALISCHE CHEMIE NEUE FOLGE | 1990年 / 166卷
关键词
Energy transfer; Kinetics; Photochemistry; UV Spectroscopy;
D O I
10.1524/zpch.1990.166.Part_2.129
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
Vibrationally highly excited C6F6 molecules in the electronic ground state (excitation energy <E> = 53270 cm-1) were prepared by electronic excitation via light absorption at 193 nm followed by internal conversion. The stepwise deactivation of the excited molecules in collisions with inert bath gases was monitored by time-resolved “hot” UV absorption spectroscopy at 230 nm and 290 nm. Absorption signals were converted into energy-loss profiles using energy dependent absorption coefficients at 230 nm and 290 nm which were calibrated in separate shock wave and laser excitation experiments. The experimental profiles were analyzed in terms of average energies transferred per collision <ΔE>. For the same collision partners, collisional deactivation was found to be about 4 times more efficient in C6F6 than in hydrocarbons of similar size such as benzene and toluene. © by R. Oldenbourg Verlag
引用
收藏
页码:129 / 143
页数:15
相关论文
共 38 条
[2]   TEMPERATURE-DEPENDENT ENERGY-TRANSFER - DIRECT EXPERIMENTS USING AZULENE [J].
BARKER, JR ;
GOLDEN, RE .
JOURNAL OF PHYSICAL CHEMISTRY, 1984, 88 (05) :1012-1017
[3]  
BRAND U, IN PRESS
[4]   MEASUREMENT OF INTERNAL ENERGIES BY HOT ULTRAVIOLET-ABSORPTION SPECTROSCOPY - SPECTRA OF EXCITED AZULENE MOLECULES [J].
BROUWER, L ;
HIPPLER, H ;
LINDEMANN, L ;
TROE, J .
JOURNAL OF PHYSICAL CHEMISTRY, 1985, 89 (21) :4608-4612
[5]   AN ACTIVE-MODE IN BOTH THE COLLISION-FREE AND COLLISION-INDUCED VIBRATIONAL DYNAMICS OF S-1 P-DIFLUOROBENZENE [J].
CATLETT, DL ;
HOLTZCLAW, KW ;
KRAJNOVICH, D ;
MOSS, DB ;
PARMENTER, CS ;
LAWRANCE, WD ;
KNIGHT, AEW .
JOURNAL OF PHYSICAL CHEMISTRY, 1985, 89 (09) :1577-1581
[6]   HIGH-PRESSURE FALLOFF CURVES AND SPECIFIC RATE CONSTANTS FOR THE REACTIONS H + O2 REVERSIBLE HO2 REVERSIBLE HO + O [J].
COBOS, CJ ;
HIPPLER, H ;
TROE, J .
JOURNAL OF PHYSICAL CHEMISTRY, 1985, 89 (02) :342-349
[7]   VIBRATIONAL FORCE-FIELD OF HALOGENATED AROMATIC-MOLECULES - IN-PLANE VIBRATIONS OF BENZENE AND FLUOROBENZENES [J].
EATON, VJ ;
STEELE, D .
JOURNAL OF MOLECULAR SPECTROSCOPY, 1973, 48 (03) :446-458
[9]   COLLISIONAL DEACTIVATION OF VIBRATIONALLY HIGHLY EXCITED POLYATOMIC-MOLECULES .4. TEMPERATURE-DEPENDENCE OF [DELTA-E] [J].
HEYMANN, M ;
HIPPLER, H ;
TROE, J .
JOURNAL OF CHEMICAL PHYSICS, 1984, 80 (05) :1853-1860
[10]   COLLISIONAL ENERGY-TRANSFER OF VIBRATIONALLY HIGHLY EXCITED MOLECULES .6. ENERGY-DEPENDENCE OF (DELTA-E) IN AZULENE [J].
HIPPLER, H ;
OTTO, B ;
TROE, J .
BERICHTE DER BUNSEN-GESELLSCHAFT-PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 1989, 93 (04) :428-434