EXCITONIC INTERACTIONS IN NAPHTHALENE CLUSTERS

被引:59
作者
WESSEL, JE
SYAGE, JA
机构
[1] Aerospace Corporation, Los Angeles, CA 90009
关键词
D O I
10.1021/j100365a042
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
Well-resolved vibronic spectra, recorded by resonance two-photon ionization, are analyzed for cold naphthalene cluster species. Spectra for isotopically pure tetramers and both pure and mixed isotopic trimer clusters provide information on resonant (excitonlike) interactions. An analysis of the spectra suggests that the tetramer geometry resembles bulk crystalline naphthalene, whereas the trimer structure minimizes direct contact interactions. Cluster geometry is similar in ground and excited states of these clusters and there is no direct evidence for rapid dynamics in the excited states, nor is there evidence of multiple geometric conformations. Analysis of the isotopically mixed trimers suggests a preference for the HDH conformation, rather than HHD. An empirical weak interaction model provides a successful descripton of the observed spectra. Excitonic splittings are approximately proportional to dipole transition strengths for the vibronically induced spectra, whereas low-intensity allowed origin transitions exhibit splittings that greatly exceed dipolar contributions. Both results indicte that the long-range intermolecular potential exceeds simple estimates. This method of analysis may be applicable to studies of larger clusters, providing new information on size-dependent structure and dynamics. © 1990 American Chemical Society.
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页码:737 / 747
页数:11
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