Density functional calculations on electronic circular dichroism spectra of chiral transition metal complexes

被引:82
作者
Autschbach, J
Jorge, FE
Zlegler, T
机构
[1] Univ Calgary, Dept Chem, Calgary, AB T2N 1N4, Canada
[2] Univ Fed Espirito Santo, Dept Fis, BR-29060900 Vitoria, ES, Brazil
关键词
D O I
10.1021/ic020580w
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Time-dependent density functional theory (TD-DFT) has for the first time been applied to the computation of circular dichroism (CD) spectra of transition metal complexes, and a detailed comparison with experimental spectra has been made. Absorption spectra are also reported. Various Co-III complexes as well as [Rh(en)(3)](3+) are studied in this work. The resulting simulated CD spectra are generally in good agreement with experimental spectra after corrections for systematic errors in a few of the lowest excitation energies are applied. This allows for an interpretation and assignment of the spectra for the whole experimentally accessible energy range (UV/vis). Solvent effects on the excitations are estimated via inclusion of a continuum solvent model. This significantly improves the computed excitation energies for charge-transfer bands for complexes of charge +3, but has only a small effect on those for neutral or singly charged complexes. The energies of the weak d-to-d transitions of the Co complexes are systematically overestimated due to deficiencies of the density functionals. These errors are much smaller for the 4d metal complex. Taking these systematic errors and the effect of a solvent into consideration, TD-DFT computations are demonstrated to be a reliable tool in order to assist with the assignment and interpretation of CD spectra of chiral transition metal complexes.
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收藏
页码:2867 / 2877
页数:11
相关论文
共 89 条
[1]  
[Anonymous], 1995, RECENT ADV DENSITY 1
[2]   Chiroptical properties from time-dependent density functional theory. II. Optical rotations of small to medium sized organic molecules [J].
Autschbach, J ;
Patchkovskii, S ;
Ziegler, T ;
van Gisbergen, SJA ;
Baerends, EJ .
JOURNAL OF CHEMICAL PHYSICS, 2002, 117 (02) :581-592
[3]   Calculating molecular electric and magnetic properties from time-dependent density functional response theory [J].
Autschbach, J ;
Ziegler, T .
JOURNAL OF CHEMICAL PHYSICS, 2002, 116 (03) :891-896
[4]   Chiroptical properties from time-dependent density functional theory. I. Circular dichroism spectra of organic molecules [J].
Autschbach, J ;
Ziegler, T ;
van Gisbergen, SJA ;
Baerends, EJ .
JOURNAL OF CHEMICAL PHYSICS, 2002, 116 (16) :6930-6940
[5]  
AUTSCHBACH J, IN PRESS
[6]  
AUTSCHBACH J, UNPUB
[7]   Density functional theory study of redox pairs. 1. Dinuclear iron complexes that undergo multielectron redox reactions accompanied by a reversible structural change [J].
Baik, MH ;
Ziegler, T ;
Schauer, CK .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (38) :9143-9154
[8]  
Ballhausen C. J., 1979, MOL ELECT STRUCTURES
[9]   Treatment of electronic excitations within the adiabatic approximation of time dependent density functional theory [J].
Bauernschmitt, R ;
Ahlrichs, R .
CHEMICAL PHYSICS LETTERS, 1996, 256 (4-5) :454-464
[10]   CONFORMATIONAL ANALYSIS OF TRIS(ETHYLENEDIAMINE) COMPLEXES [J].
BEATTIE, JK .
ACCOUNTS OF CHEMICAL RESEARCH, 1971, 4 (07) :253-&