HIGH-PRESSURE EFFECT ON THE TWISTED INTRAMOLECULAR CHARGE-TRANSFER FLUORESCENCE AND ABSORPTION OF PARA-N,N-DIMETHYLAMINOBENZYLIDENEMALONONITRILE (DMABMN) IN POLYMERIC MATRICES

被引:18
作者
DREGER, ZA
LANG, JM
DRICKAMER, HG
机构
[1] UNIV ILLINOIS,SCH CHEM SCI,DEPT PHYS,URBANA,IL 61801
[2] UNIV ILLINOIS,MAT RES LAB,URBANA,IL 61801
关键词
D O I
10.1016/0301-0104(92)87018-5
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 pressure effect on the luminescence of p-N,N-dimethylaminobenzylidenemalononitrile (DMABMN) in several solid polymer matrices has been studied. An increase of fluorescence intensity by a factor of 35 to 200 has been observed, in different polymers, within 100 kbar. Two general regions of pressure behavior are distinguished. In the first, "low pressure" region (0-25) kbar the amplification of luminescence intensity is explained by a retardation of motion (twist) in the excited state by increasing pressure. The generalized volume change "DELTAV" for this process has been obtained as a function of pressure and could be predicted from the kinetic model proposed. The polarity and free volume effects are discussed. The free volume concept is found not to provide a satisfactory quantitative description for the pressure dependence of the rearrangement. In the "high pressure" region (> 50 kbar) where intensity decreases to a different degree in different polymers the contribution of the nonradiative rate from the originally excited state is considered.
引用
收藏
页码:193 / 206
页数:14
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