FROM MONOMERS TO CLUSTERS - PHOTODISSOCIATION OF TERT-BUTYL NITRITE (CH3)(3)CONO AND HOMOGENEOUS [(CH3)(3)CONO](N) CLUSTERS

被引:31
作者
KADES, E [1 ]
ROSSLEIN, M [1 ]
HUBER, JR [1 ]
机构
[1] UNIV ZURICH, INST PHYS CHEM, CH-8057 ZURICH, SWITZERLAND
关键词
D O I
10.1021/j100102a021
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
Homogeneous and neutral clusters of tert-butyl nitrite [(CH3)(3)CONO](n), with (n) roughly 20, were produced by adiabatic jet expansion and photolyzed via the localized S-1(n pi(*)) <-- S-0 transition to R + NO ((2) Pi) at lambda(d) approximate to 360-400 nm. Using photofragment yield spectroscopy (PHOFRY), we determined the relative partial absorption cross sections leading to NO (nu'' = 0, 1, 2) products from the monomer and the clusters which allowed us to selectively investigate from a monomer/ cluster mixture the cluster formation and the cluster photodissociation. The latter was further characterized by the rotational state distributions of the four sublevels of NO ((2) Pi(+/-1/2) and (2) Pi(+/-3/2)) and the rotational alignment A(0)(2)). Essentially two types of NO fragments emerged from the photoexcited clusters: one having relaxed J state distributions and no alignment A(0)((2)), the other hot (non-Boltzmann) distributions and a strong alignment as well as a preference for the Lambda-state A''. The relaxed NO fragments are proposed to arise from nitrite molecules ''solvated'' in the cluster and the hot NO fragments from nitrite molecules with a free chromophore located on the surface of the cluster. The vibrational state population of NO appears no to be significantly influenced by cluster formation.
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页码:13556 / 13562
页数:7
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