ELECTRONIC-SPECTRA OF JET-COOLED 5-BROMOTROPOLONE AND 5-CHLOROTROPOLONE - INFLUENCE OF SYMMETRICAL SUBSTITUTION ON PROTON TUNNELING IN THE S1 STATE

被引：42

作者：

TSUJI, T ^{[1
]}

SEKIYA, H ^{[1
]}

NISHIMURA, Y ^{[1
]}

MORI, R ^{[1
]}

MORI, A ^{[1
]}

TAKESHITA, H ^{[1
]}

机构：

[1] KYUSHU UNIV,GRAD SCH ENGN SCI,DEPT MOLEC SCI & TECHNOL,KASUGA,FUKUOKA 816,JAPAN

来源：

JOURNAL OF CHEMICAL PHYSICS | 1992年 / 97卷 / 09期

关键词：

D O I：

10.1063/1.463713

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 S1-S0 fluorescence excitation and dispersed fluorescence spectra have been measured for jet-cooled 5-bromotropolone (5BTR-h), 5-chlorotropolone (5CTR-h), and their OD derivatives in order to investigate substituent effects on proton tunneling. Both the 0++ and 0-- transitions were identified in the fluorescence spectra of these molecules. The tunneling doublet splittings in the electronic origin band of 5BTR-h (16 cm-1) decreased by 4 cm-1, whereas that of 5CTR-h (23 cm-1) increased by 3 cm-1 as compared with tropolone (TRN-h). Relatively small deviation in the tunneling separations for these molecules from that for tropolone is ascribed to conjugation in the S1 state. An electron-withdrawing character of chlorine and bromine atoms is almost canceled by a conjugative electron-releasing effect.

引用

页码：6032 / 6039

页数：8

共 32 条

[1] NEAR ULTRAVIOLET-SPECTRUM OF TROPOLONE VAPOR AND ITS RELEVANCE TO MOLECULAR STRUCTURE .1. ROTATIONAL BAND CONTOUR ANALYSIS [J].