VIBRATIONAL CIRCULAR-DICHROISM OF PROPYLENE-OXIDE

被引:30
作者
KAWIECKI, RW
DEVLIN, FJ
STEPHENS, PJ
AMOS, RD
机构
[1] UNIV CAMBRIDGE,DEPT THEORET CHEM,CAMBRIDGE CB2 1EW,ENGLAND
[2] UNIV SO CALIF,DEPT CHEM,LOS ANGELES,CA 90089
基金
美国国家科学基金会; 美国国家卫生研究院;
关键词
D O I
10.1021/j100177a040
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
Vibrational absorption and circular dichroism spectra of neat liquid and CS2 and CCl4 solutions of propylene oxide are reported. Scaled quantum-mechanical (SQM) force fields are derived from absorption frequencies together with ab initio SCF calculations using the STO-3G, 4-31G, 6-31G*, and 6-31G** basis sets. Absorption and VCD spectra are calculated using these force fields and ab initio SCF atomic polar and axial tensors obtained using analytical derivative methods and STO-3G, 4-31G, 6-31G*, 6-31G**, DZ/1P, and 6-311G** basis sets. Atomic axial tensors are calculated using two choices of gauge. Calculated spectra are in generally excellent agreement with experiment when basis sets of sufficient size are used for the calculation of force fields and atomic polar and axial tensors and when the distributed origin gauge is used. Agreement is less satisfactory in spectral regions where vibrational transitions are closely spaced and where Fermi resonance is substantial. The results support the conclusion that generally reliable predictions of VCD spectra can be obtained using Stephens' equation for vibrational rotational strengths together with molecular geometries, vibrational force fields, and atomic polar and axial tensors derived via ab initio SCF calculations.
引用
收藏
页码:9817 / 9831
页数:15
相关论文
共 44 条
[1]   EFFICIENT CALCULATION OF VIBRATIONAL MAGNETIC DIPOLE TRANSITION MOMENTS AND ROTATIONAL STRENGTHS [J].
AMOS, RD ;
HANDY, NC ;
JALKANEN, KJ ;
STEPHENS, PJ .
CHEMICAL PHYSICS LETTERS, 1987, 133 (01) :21-26
[2]  
BARRON LD, 1982, MOL LIGHT SCATTERING, pCH7
[3]  
BENHEGYI G, 1982, THEOCHEM, V89, P1
[4]   APPLICATION OF SELF-CONSISTENT-FIELD AB-INITIO CALCULATIONS TO ORGANIC-MOLECULES .1. EQUILIBRIUM STRUCTURE AND FORCE CONSTANTS OF HYDROCARBONS [J].
BLOM, CE ;
SLINGERLAND, PJ ;
ALTONA, C .
MOLECULAR PHYSICS, 1976, 31 (05) :1359-1376
[5]   VIBRATIONAL CIRCULAR-DICHROISM MEASUREMENT IN THE FREQUENCY-RANGE OF 800 TO 650 CM-1 [J].
DEVLIN, F ;
STEPHENS, PJ .
APPLIED SPECTROSCOPY, 1987, 41 (07) :1142-1144
[6]  
DEVLIN FJ, IN PRESS
[8]  
Fogarasi G., 1985, Vibrational spectra and structure. A Series of Advances. Vol.14, P125
[9]   VIBRATIONAL OPTICAL-ACTIVITY CALCULATIONS USING INFRARED AND RAMAN ATOMIC POLAR TENSORS [J].
FREEDMAN, TB ;
NAFIE, LA .
JOURNAL OF CHEMICAL PHYSICS, 1983, 78 (01) :27-31
[10]   STEREOCHEMICAL ASPECTS OF VIBRATIONAL OPTICAL-ACTIVITY [J].
FREEDMAN, TB ;
NAFIE, LA .
TOPICS IN STEREOCHEMISTRY, 1987, 17 :113-206