Chiroptical properties from time-dependent density functional theory. II. Optical rotations of small to medium sized organic molecules

被引:166
作者
Autschbach, J
Patchkovskii, S
Ziegler, T
van Gisbergen, SJA
Baerends, EJ
机构
[1] Univ Calgary, Dept Chem, Calgary, AB T2N 1N4, Canada
[2] Free Univ Amsterdam, FEW, NL-1081 HV Amsterdam, Netherlands
关键词
D O I
10.1063/1.1477925
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
We report an implementation for the computation of optical rotations within the Amsterdam Density Functional program package. The code is based on time-dependent density functional response theory. Optical rotations have been calculated for a test set of 36 organic molecules with various density functionals, and employing basis sets of different quality. The results obtained in this work with nonhybrid functionals are comparable in quality to those recently reported by other authors for the B3LYP hybrid functional, but show a somewhat larger tendency to produce outlyers. The median error is approximately 20degrees/(dm g/cm(3)) for specific rotations [alpha](D) as compared to experimental data (approximately 30% median deviation from experimental values). Thereby it is demonstrated that density functional computations can be employed to assist with the solution of stereochemical problems in case the specific rotations of the species involved are not small and their structures are rigid. Recent newly developed functionals are investigated with respect to their applicability in computations of optical rotations. (C) 2002 American Institute of Physics.
引用
收藏
页码:581 / 592
页数:12
相关论文
共 50 条
[1]  
[Anonymous], 1995, RECENT ADV DENSITY 1
[2]  
[Anonymous], [No title captured], DOI DOI 10.1016/0021-9991(92)90277-6
[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]   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
[6]   DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].
BECKE, AD .
PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100
[7]   COMPOUNDS WITH A HELIX STRUCTURE .1. SYNTHESIS AND ABSOLUTE-CONFIGURATION OF (+)-PENTAHELICENE [J].
BESTMANN, HJ ;
BOTH, W .
CHEMISCHE BERICHTE-RECUEIL, 1974, 107 (09) :2923-2925
[8]   PI-ELECTRON ABSORPTION AND CIRCULAR DICHROISM SPECTRA OF [6]-HELICENE AND [7]-HELICENE [J].
BRICKELL, WS ;
BROWN, A ;
KEMP, CM ;
MASON, SF .
JOURNAL OF THE CHEMICAL SOCIETY A -INORGANIC PHYSICAL THEORETICAL, 1971, (05) :756-&
[9]  
Buckingham A. D., 1967, ADV CHEM PHYS, V12, P107, DOI DOI 10.1002/9780470143582.CH2
[10]   EXPERIMENTAL AND QUANTUM-THEORETICAL INVESTIGATION OF THE CIRCULAR-DICHROISM SPECTRUM OF R-METHYLOXIRANE [J].
CARNELL, M ;
PEYERIMHOFF, SD ;
BREEST, A ;
GODDERZ, KH ;
OCHMANN, P ;
HORMES, J .
CHEMICAL PHYSICS LETTERS, 1991, 180 (05) :477-481