INTRAMOLECULAR ASPECTS OF THE ELECTRON-TRANSFER IN THE BIFERROCENIUM MIXED-VALENCE CATION, USING PKS THEORY

被引:21
作者
BOUKHEDDADEN, K [1 ]
LINARES, J [1 ]
BOUSSEKSOU, A [1 ]
NASSER, J [1 ]
RABAH, H [1 ]
VARRET, F [1 ]
机构
[1] UNIV MAINE,PHYS MAT LAB,CNRS,URA 807,F-72017 LE MANS,FRANCE
关键词
D O I
10.1016/0301-0104(93)80091-M
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 electron transfer properties of the mixed-valence biferrocenium cation are investigated using the Piepho-Krausz-Schatz (PKS) vibronic theory. Parameters of the model are deduced from both vibrational spectroscopy (stiffness constant) and MO calculations (transfer integral and vibronic coupling parameter); the computed asymmetric distortion agrees with structural data; a specific heat Schottky anomaly, recently reported, is also explained in the frame of that model. The low-temperature transfer rate is also computed. It ranges from 1.5 x 10(10) to 8.7 x 10(12) s-1, according to the nature of the HOMO, and definitively lies higher than the Mossbauer timescale (almost-equal-to 10(8) s-1).
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页码:47 / 55
页数:9
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