ABINITIO CALCULATIONS ON THE LOWER EXCITED-STATES OF SHORT-CHAIN POLYENALS

被引：6

作者：

ROS, M

GROENEN, EJJ

VANHEMERT, MC

机构：

[1] LEIDEN UNIV,CTR STUDY EXCITED STATES MOLEC,HUYGENS LAB,POB 9504,2312 AV LEIDEN,NETHERLANDS

[2] LEIDEN UNIV,GORLAEUS LABS,DEPT CHEM,2300 RA LEIDEN,NETHERLANDS

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1992年 / 114卷 / 17期

关键词：

D O I：

10.1021/ja00043a030

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The lower excited states of the planar all-trans isomers of crotonaldehyde, hexadienal, and octatrienal have been investigated by multi-reference single and double excitation configuration interaction (MRD-CI) calculations. For crotonaldehyde we find both the lowest excited singlet state S1 and the lowest triplet state T0 to be n-pi* in nature; for hexadienal and octatrienal S1 is n-pi* and T0 is pi-pi* in nature. Bond-order reversal stabilizes the lower excited states and destabilizes the ground state. The pi-pi* states decrease more in energy than the n-pi* states upon lengthening the polyenal. We calculate the radiative lifetime of the 3-pi-pi* state in the ground-state geometry to vary from 35 ms for crotonaldehyde to 75 s for octatrienal and explain the absence of phosphorescence for polyenals.

引用

页码：6820 / 6827

页数：8

共 33 条

[31] MICROWAVE SPECTRUM, BARRIER TO INTERNAL ROTATION, AND DIPOLE MOMENT OF TRANS-CROTONALDEHYDE [J].