ELECTRONIC-SPECTRUM OF ALLYL AND ALLYL-D5 RADICALS - THE B[1(2)A1][-X[1(2)A2], C[2(2)B1][-X[1(2)A2], AND D[1(2)B2][-X[1(2)A2] BAND SYSTEMS

被引：54

作者：

BLUSH, JA ^{[1
]}

MINSEK, DW ^{[1
]}

CHEN, P ^{[1
]}

机构：

[1] HARVARD UNIV,MALLINCKRODT CHEM LAB,CAMBRIDGE,MA 02138

来源：

JOURNAL OF PHYSICAL CHEMISTRY | 1992年 / 96卷 / 25期

关键词：

D O I：

10.1021/j100204a013

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：

Three electronic band systems, D[1B-2(2)] <-- X[1(2)A2], C[2B-2(1)] <-- X[1(2)A2], and B[1(2)A1] <-- X[1(2)A2], are found and analyzed for both C3H5 and C3D5 between 238 and 250 nm by resonant 1+1 multiphoton ionization. Partially-resolved rotational structure is simulated and fit to determine the upper-state vibronic symmetry of each band. Assignment of each band was then done using symmetry, isotope shift, and normal-mode information. The appearance of nominally forbidden bands in the B[1(2)A1] <-- X[1(2)A2] system is rationalized by the proposed nonplanarity of the upper state of the transition. The resulting double-well potential causes large inversion doubling of B-state levels, which explains anomalies in both the 1+1 and 2+2 MPI spectra of allyl radical.

引用

页码：10150 / 10154

页数：5

共 29 条

[1] PHOTOELECTRON-SPECTRUM OF THE VINYL RADICAL - DOWNWARD REVISION OF THE C2H3 IONIZATION-POTENTIAL [J].