THEORETICAL-STUDY OF THE LOW-LYING STATES OF TRANS-1,3-BUTADIENE

被引:42
作者
SERRANOANDRES, L
SANCHEZMARIN, J
NEBOTGIL, I
机构
[1] Departament de Química Física, Universitat de València, 46100-Burjassot, Valencia
关键词
D O I
10.1063/1.463521
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 present extensive ab initio calculations on the low-lying electronic states of trans-1,3-butadiene within the multireference configuration interaction (MRCI) framework by selecting the configurations with a perturbative criterion. The X 1A(g) ground state and 1 B-3u, 1 3A(g), 2 1A(g), and 1 B1-u valence excited states have been calculated at a fixed geometry. The results obtained are in good agreement with previous experimental and calculated values, and could help to understand polyene spectroscopy, photochemistry, and photophysics. The advantages of a MRCI method where the most important contributions to the total MRCI wave function, perturbatively selected, are treated variationally, and the remaining terms are evaluated by means of a perturbational approach, are also discussed. Furthermore, a criterion in order to build a correlation-consistent configuration interaction space is stated and, therefore, a reliable approximation to achieve accurate energy differences is obtained. Several monoelectronic molecular-orbital basis functions are tried in order to select the most adequate to describe each state.
引用
收藏
页码:7499 / 7506
页数:8
相关论文
共 79 条
[1]   AN MCSCF STUDY OF THE LOW-LYING STATES OF TRANS-BUTADIENE [J].
AOYAGI, M ;
OSAMURA, Y ;
IWATA, S .
JOURNAL OF CHEMICAL PHYSICS, 1985, 83 (03) :1140-1148
[2]   CI STUDY OF GEOMETRICAL RELAXATION IN THE EXCITED-STATES OF BUTADIENE - ENERGY SURFACES AND PROPERTIES FOR SIMULTANEOUS TORSION AND ELONGATION OF ONE DOUBLE-BOND [J].
BONACICKOUTECKY, V ;
PERSICO, M ;
DOHNERT, D ;
SEVIN, A .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1982, 104 (25) :6900-6907
[3]  
BRONGERSMA HH, 1967, FAST REACT PRIMARY, P211
[4]   ALL-VALENCE-ELECTRON CI TREATMENT OF ELECTRONIC-SPECTRUM OF TRANS-BUTADIENE [J].
BUENKER, RJ ;
SHIH, S ;
PEYERIMHOFF, SD .
CHEMICAL PHYSICS LETTERS, 1976, 44 (02) :385-393
[5]   LOCATION OF THE 21AG STATE IN HEXATRIENE [J].
BUMA, WJ ;
KOHLER, BE ;
SONG, K .
JOURNAL OF CHEMICAL PHYSICS, 1990, 92 (07) :4622-4623
[6]   LOWEST ENERGY EXCITED SINGLET-STATE OF ISOLATED CIS-HEXATRIENE [J].
BUMA, WJ ;
KOHLER, BE ;
SONG, K .
JOURNAL OF CHEMICAL PHYSICS, 1991, 94 (10) :6367-6376
[7]   ELEMENTARY UNITARY MO TRANSFORMATIONS AND SCF THEORY [J].
CARBO, R ;
DOMINGO, L ;
PERIS, JJ .
ADVANCES IN QUANTUM CHEMISTRY, 1982, 15 :215-265
[8]  
CARBO R, 1983, J MOL STRUC-THEOCHEM, V10, P15, DOI 10.1016/0166-1280(83)80089-X
[9]   BONDING IN TRANSITION-METAL-METHYLENE COMPLEXES .2. (RUCH2)+, A COMPLEX EXHIBITING LOW-LYING METHYLIDENE-LIKE AND CARBENE-LIKE STATES [J].
CARTER, EA ;
GODDARD, WA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (09) :2180-2191
[10]   NEW PREDICTIONS FOR SINGLET TRIPLET GAPS OF SUBSTITUTED CARBENES [J].
CARTER, EA ;
GODDARD, WA .
JOURNAL OF PHYSICAL CHEMISTRY, 1987, 91 (18) :4651-4652