Theoretical study of valence and Rydberg excited states of benzene revisited

被引：43

作者：

Hashimoto, T ^{[1
]}

Nakano, H ^{[1
]}

Hirao, K ^{[1
]}

机构：

[1] Univ Tokyo, Grad Sch Engn, Dept Appl Chem, Tokyo 113, Japan

来源：

THEOCHEM-JOURNAL OF MOLECULAR STRUCTURE | 1998年 / 451卷 / 1-2期

关键词：

benzene; valence excited states; Rydberg excited states;

D O I：

10.1016/S0166-1280(98)00156-0

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：

The multireference Moller-Plesset perturbation (MRMP) theory with complete active space self-consistent field (CASSCF) reference functions is applied to the study of the singlet and tripler valence pi-pi* excited states and Rydberg excited states of benzene in the ultraviolet region. The overall accuracy of MRMP is surprisingly high. The average deviations of the excitation energies from the available experimental values are 0.1 eV for the valence excited slates and 0.15 eV for the Rydberg states. A comparison is made with recent results of single reference-based methods. It is concluded that MRMP is able to describe satisfactorily excited states with a double excitation character, while single reference-based methods are not. (C) 1998 Elsevier Science B.V. All rights reserved.

引用

页码：25 / 33

页数：9

共 24 条

[1] First allowed triplet-triplet transition in benzene [J].

Astier, R. ;

Meyer, Y. H. .

CHEMICAL PHYSICS LETTERS, 1969, 3 (06) :399-401

[2] Large-scale calculations of excitation energies in coupled cluster theory: The singlet excited states of benzene [J].

Christiansen, O ;

Koch, H ;

Halkier, A ;

Jorgensen, P ;

Helgaker, T ;

deMeras, AS .

JOURNAL OF CHEMICAL PHYSICS, 1996, 105 (16) :6921-6939

[3] Coupled-cluster calculations of the excitation energies of benzene and the azabenzenes [J].

DelBene, JE ;

Watts, JD ;

Bartlett, RJ .

JOURNAL OF CHEMICAL PHYSICS, 1997, 106 (14) :6051-6060

[4] LOW-ENERGY ELECTRON-IMPACT STUDY OF FIRST, SECOND, AND THIRD TRIPLET STATES OF BENZENE [J].

DOERING, JP .

JOURNAL OF CHEMICAL PHYSICS, 1969, 51 (07) :2866-&

[5] GAUSSIAN-BASIS SETS FOR USE IN CORRELATED MOLECULAR CALCULATIONS .1. THE ATOMS BORON THROUGH NEON AND HYDROGEN [J].

DUNNING, TH .

JOURNAL OF CHEMICAL PHYSICS, 1989, 90 (02) :1007-1023

[6] A PRECISE DETERMINATION OF THE 1ST IONIZATION-POTENTIAL OF BENZENE [J].

GRUBB, SG ;

WHETTEN, RL ;

ALBRECHT, AC ;

GRANT, ER .

CHEMICAL PHYSICS LETTERS, 1984, 108 (05) :420-424

[7] Theoretical study of the valence pi->pi* excited states of polyacenes: Benzene and naphthalene [J].

Hashimoto, T ;

Nakano, H ;

Hirao, K .

JOURNAL OF CHEMICAL PHYSICS, 1996, 104 (16) :6244-6258

[8] MULTIREFERENCE MOLLER-PLESSET METHOD [J].

HIRAO, K .

CHEMICAL PHYSICS LETTERS, 1992, 190 (3-4) :374-380

[9] MULTIREFERENCE MOLLER-PLESSET PERTURBATION TREATMENT FOR VALENCE AND RYDBERG EXCITED-STATES OF BENZENE [J].

HIRAO, K ;

NAKANO, H ;

HASHIMOTO, T .

CHEMICAL PHYSICS LETTERS, 1995, 235 (5-6) :430-435

[10] DIRECT ABSORPTION-SPECTRA OF JET-COOLED BENZENE IN 130-260-NM [J].

HIRAYA, A ;

SHOBATAKE, K .

JOURNAL OF CHEMICAL PHYSICS, 1991, 94 (12) :7700-7706

← 1 2 3 →