VIBRONIC INTENSITIES IN THE ELECTRONIC-SPECTRA OF TRANSITION-METAL COMPLEX-IONS .8. VIBRATIONAL COORDINATES FOR OCTAHEDRAL IONS AND THEIR APPLICATION TO THE A-4(2G) REVERSIBLE E-2(G) TRANSITION OF THE MNF6(2-) ION

被引：8

作者：

ACEVEDO, R ^{[1
]}

DIAZ, G ^{[1
]}

VASQUEZ, SO ^{[1
]}

FLINT, CD ^{[1
]}

机构：

[1] UNIV LONDON,BIRKBECK COLL,DEPT CHEM,LASER LAB,LONDON WC1H 0PP,ENGLAND

来源：

THEORETICA CHIMICA ACTA | 1991年 / 79卷 / 05期

关键词：

VIBRONIC INTENSITIES; VIBRATIONAL COORDINATES; CRYSTAL FIELD; LIGAND POLARIZATION; COMPLEX ION;

D O I：

10.1007/BF01114693

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：

A reexamination of the vibrational coordinates appropriate in vibronic intensity calculations in octahedral coordination compounds is presented. We derive a complete set of symmetry coordinates that is orthonormal and transforms correctly under the group generators. The vibronic hamiltonian for the crystal field and ligand polarization contributions to the intensity are calculated in the basis of these coordinates. The crystal field term is evaluated both using a truncated basis set for the intermediate electronic states and using the closure approximation. These methods have been applied to the calculation of the vibronic intensity distribution for the 4A2g <--> 2E(g) transition of the MnF6(2-) ion and close agreement wtih experiment achieved.

引用

页码：349 / 360

页数：12