TIME-RESOLVED RESONANCE RAMAN-SPECTROSCOPY OF DIPHENYLACETYLENE - STRUCTURES AND DYNAMICS OF THE LOWEST EXCITED TRIPLET-STATE, RADICAL CATION, AND RADICAL-ANION

被引：36

作者：

HIURA, H ^{[1
]}

TAKAHASHI, H ^{[1
]}

机构：

[1] WASEDA UNIV,SCH SCI & ENGN,DEPT CHEM,TOKYO 169,JAPAN

来源：

JOURNAL OF PHYSICAL CHEMISTRY | 1992年 / 96卷 / 22期

关键词：

D O I：

10.1021/j100201a040

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：

Time-resolved resonance Raman spectra of the lowest excited triplet state, T1, the radical cation, R.+, and the radical anion, R.-, of diphenylacetylene (DPA) have been measured. Vibrational assignments of the Raman bands of these transients have been made based on the frequency shifts on phenyl deuterations and C-13 substitution of the C=C triple bond. The Raman spectra have shown that the C=C stretch exhibits large low-frequency shifts in the order, S0 (2217 cm-1), R.+ (2142 cm-1), R.- (2091 cm-1), and T1 (1972 cm-1), indicating that the C=C triple bond weakens dramatically in this sequence. The same trend, though not large, has been observed for phenyl skeletal vibrations as well. The dependence of the yield of R.+ on the pump laser power has revealed that the photoionization of DPA to produce R.+ is a biphotonic process, and sensitized photoexcitation at 360 nm using benzophenone as a triplet sensitizer has disclosed that biphotonic ionization can occur through the T1 state.

引用

页码：8909 / 8915

页数：7

共 22 条

[1] THERMAL STEREOMUTATIONS OF (2R,3R)-PHENYLCYCLOPROPANE-1,2,3-H-2(3) AND (1R,2S,3R)-PHENYLCYCLOPROPANE-2-C-13-1,2,3-2H3 - QUANTIFICATION OF ALL 4 STEREOCHEMICAL MODES FOR INTERCONVERSIONS AMONG THE 1-PHENYL-1,2,3-TRIDEUTERIOCYCLOPROPANES [J].