HIGH-RESOLUTION SPECTROSCOPY OF JET-COOLED SUBSTITUTED CYCLOPENTADIENYL RADICALS

被引：10

作者：

CULLIN, DW ^{[1
]}

YU, L ^{[1
]}

WILLIAMSON, JM ^{[1
]}

MILLER, TA ^{[1
]}

机构：

[1] OHIO STATE UNIV,DEPT CHEM,LASER SPECT FACIL,120 W 18TH AVE,COLUMBUS,OH 43210

来源：

JOURNAL OF PHYSICAL CHEMISTRY | 1992年 / 96卷 / 01期

关键词：

D O I：

10.1021/j100180a020

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：

Rotationally resolved electronic spectra have been observed for a number of substituted cyclopentadienyl radicals, C5H4X, with X = F, Cl, CN, and CH3. This paper reports the spectral analysis for the radicals with X = F and Cl; results for X = CN and CH3 have been reported previously. The geometric structural parameters for all the radicals are consistent with a distortion of the five-membered ring to a diene-like structure in the ground state, with C-C bond length alternations in excess of 0.1 angstrom in some cases. The analysis also quite clearly shows a strengthening and shortening of the C-X bond in the radical compared to that of the similarly substituted benzene derivatives. The observed results are rationalized in terms of a simple molecular orbital picture involving conjugation and hyperconjugation.

引用

页码：89 / 94

页数：6