INTRAMOLECULAR VIBRATIONAL DYNAMICS OF DIACETYLENE AND DIACETYLENE-D(1) VIA EIGENSTATE-RESOLVED OVERTONE SPECTROSCOPY

被引:19
作者
GAMBOGI, JE
PEARSON, RZ
YANG, XM
LEHMANN, KK
SCOLES, G
机构
[1] Department of Chemistry, Princeton University, Princeton
基金
美国国家科学基金会;
关键词
D O I
10.1016/0301-0104(95)91250-L
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 high resolution spectra of several CH overtone bands in diacetylene and diacetylene-d, were measured using optothermally detected excitation of a collimated molecular beam. The first overtone of the acetylenic CH stretches in these two molecules were recorded in a single resonance scheme using a 1.5 mu m color center laser. The second overtone spectra were taken using sequential infrared/infrared double resonance with a 3.0 and a 1.5 mu m color center lasers. The perturbations in the spectra have been analyzed to obtain information about the nature and timescales of the underlying intramolecular vibrational redistribution processes. The uncovered dynamical features appear to be dominated by anharmonic couplings and exhibit regular, not chaotic, behavior. The first and second overtone spectra of diacetylene-d(1) are consistent with a coupling model which involves coupling through a doorway state and then subsequent coupling to the bath. In diacetylene, a combination band was also recorded which, in the local mode picture, is equivalent to putting two quanta in one acetylenic CH stretch and one quanta at the other end of the molecule. Comparison of this spectrum with the spectrum obtained by putting three quanta in the same CH stretch, is consistent with earlier observations that delocalized combination bands are less perturbed than nearly isoenergetic pure overtone states.
引用
收藏
页码:191 / 205
页数:15
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