VALIDATION OF SELF-CONSISTENT HYBRID DENSITY FUNCTIONALS FOR THE STUDY OF STRUCTURAL AND ELECTRONIC CHARACTERISTICS OF ORGANIC PI-RADICALS

被引:120
作者
ADAMO, C
BARONE, V
FORTUNELLI, A
机构
[1] UNIV NAPLES FEDERICO II, DIPARTIMENTO CHIM, I-80134 NAPLES, ITALY
[2] UNIV BASILICATA, DIPARTIMENTO CHIM, I-85100 POTENZA, ITALY
[3] CNR, IST CHIM QUANTIST & ENERGET MOLEC, I-56126 PISA, ITALY
关键词
D O I
10.1063/1.469413
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
Extensive density functional calculations are reported for the geometrical structures, thermochemistry, infrared, and hyperfine parameters of representative carbon-centered π radicals. Local functionals can be considered sufficient for geometrical and vibrational parameters, but seriously fail in the computation of thermochemical data and of spin-dependent properties. Gradient corrections (especially Becke exchange and Lee-Yang-Parr correlation functionals) sensibly improve matters. Inclusion of some Hartree-Fock exchange in a fully self-consistent density functional implementation delivers a further significant improvement, approaching the accuracy of the most refined post Hartree-Fock computations. Purposely tailored basis sets are also introduced which are small enough to be used in molecular computations, but still give high quality geometries and hyperfine coupling constants. © 1995 American Institute of Physics.
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页码:384 / 393
页数:10
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