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

来源：

CHEMICAL PHYSICS | 1993年 / 170卷 / 01期

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).

引用

页码：47 / 55

页数：9

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