Ab initio prediction of vibrational absorption and circular dichroism spectra of chiral natural products using density functional theory:: α-pinene

被引:116
作者
Devlin, FJ
Stephens, PJ [1 ]
Cheeseman, JR
Frisch, MJ
机构
[1] Univ So Calif, Dept Chem, Los Angeles, CA 90089 USA
[2] Lorentzian Inc, N Haven, CT 06473 USA
关键词
D O I
10.1021/jp971905a
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
Ab initio density functional theory (DFT) is used to analyze the vibrational unpolarized absorption and circular dichroism spectra of the chiral monoterpene, alpha-pinene. Large (TZ2P) basis set calculations using the hybrid functionals B3PW91 and B3LYP are in excellent overall agreement with experiment and permit the assignment of a large fraction of the fundamental frequencies, The quantitative accuracy of DFT in predicting the frequencies, dipole strengths, and rotational strengths of the fundamentals of alpha-pinene is documented for the B3PW91 and B3LYP functionals at both TZ2P and 6-31G* basis set levels. Hartree-Fock/self-consistent field (HF/SCF) calculations have also been carried out in parallel. The accuracy of the HF/SCF methodology is markedly inferior to that of DFT. In particular, HF/SCF predictions of the vibrational circular dichroism (VCD) spectrum of alpha-pinene are in very poor agreement with experiment.
引用
收藏
页码:9912 / 9924
页数:13
相关论文
共 59 条
[1]   AB-INITIO CALCULATION OF VIBRATIONAL CIRCULAR-DICHROISM SPECTRA USING GAUGE-INVARIANT ATOMIC ORBITALS [J].
BAK, KL ;
DEVLIN, FJ ;
ASHVAR, CS ;
TAYLOR, PR ;
FRISCH, MJ ;
STEPHENS, PJ .
JOURNAL OF PHYSICAL CHEMISTRY, 1995, 99 (41) :14918-14922
[2]   BASIS-SET CONVERGENCE OF ATOMIC AXIAL TENSORS OBTAINED FROM SELF-CONSISTENT-FIELD CALCULATIONS USING LONDON ATOMIC ORBITALS [J].
BAK, KL ;
JORGENSEN, P ;
HELGAKER, T ;
RUUD, K ;
JENSEN, HJA .
JOURNAL OF CHEMICAL PHYSICS, 1994, 100 (09) :6620-6627
[3]   GAUGE-ORIGIN INDEPENDENT MULTICONFIGURATIONAL SELF-CONSISTENT-FIELD THEORY FOR VIBRATIONAL CIRCULAR-DICHROISM [J].
BAK, KL ;
JORGENSEN, P ;
HELGAKER, T ;
RUUD, K ;
JENSEN, HJA .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (11) :8873-8887
[4]   A NEW MIXING OF HARTREE-FOCK AND LOCAL DENSITY-FUNCTIONAL THEORIES [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (02) :1372-1377
[5]   DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652
[6]   A comparison of models for calculating nuclear magnetic resonance shielding tensors [J].
Cheeseman, JR ;
Trucks, GW ;
Keith, TA ;
Frisch, MJ .
JOURNAL OF CHEMICAL PHYSICS, 1996, 104 (14) :5497-5509
[7]   Ab initio calculation of atomic axial tensors and vibrational rotational strengths using density functional theory [J].
Cheeseman, JR ;
Frisch, MJ ;
Devlin, FJ ;
Stephens, PJ .
CHEMICAL PHYSICS LETTERS, 1996, 252 (3-4) :211-220
[8]   NEW DESIGN FOR FOURIER-TRANSFORM INFRARED VIBRATIONAL CIRCULAR-DICHROISM SPECTROMETERS [J].
CHEN, GC ;
POLAVARAPU, PL ;
WEIBEL, S .
APPLIED SPECTROSCOPY, 1994, 48 (10) :1218-1223
[9]   Assessment of Gaussian-2 and density functional theories for the computation of enthalpies of formation [J].
Curtiss, LA ;
Raghavachari, K ;
Redfern, PC ;
Pople, JA .
JOURNAL OF CHEMICAL PHYSICS, 1997, 106 (03) :1063-1079
[10]   On the performance of density functional methods for describing atomic populations, dipole moments and infrared intensities [J].
DeProft, F ;
Martin, JML ;
Geerlings, P .
CHEMICAL PHYSICS LETTERS, 1996, 250 (3-4) :393-401