[18]Annulene: A benzene-like S-0/S-1 conical intersection located with CASSCF+GVB

被引:10
作者
Bearpark, MJ [1 ]
Bernardi, F [1 ]
Clifford, S [1 ]
Olivucci, M [1 ]
Robb, MA [1 ]
Vreven, T [1 ]
机构
[1] UNIV BOLOGNA,DIPARTIMENTO CHIM G CIAMICIAN,I-40126 BOLOGNA,ITALY
关键词
D O I
10.1080/002689796173994
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
A further parallel between the planar [18]annulene and benzene has been demonstrated: the existence of a topologically equivalent S-0/S-1 conical intersection. The lowest energy point on the crossing has been optimized with the MMBV and CASSCF + GVB/4-31G methods. These calculations suggest that fluorescence might be observed from the S-1 state of[ls]annulene, and that this would disappear at higher vibrational excess energies as a route to efficient non-radiative decay via the conical intersection became accessible (the 'channel 3' mechanism for benzene).
引用
收藏
页码:37 / 46
页数:10
相关论文
共 57 条
[1]  
Allinger NL., 1976, ADV PHYS ORG CHEM, P1, DOI 10.1016/S0065-3160(08)60212-9
[2]   THE LOW-TEMPERATURE UV./VIS. ABSORPTION-SPECTRUM OF [18]ANNULENE [J].
BAUMANN, H ;
OTH, JFM .
HELVETICA CHIMICA ACTA, 1982, 65 (06) :1885-1893
[4]   A DIRECT METHOD FOR THE LOCATION OF THE LOWEST ENERGY POINT ON A POTENTIAL SURFACE CROSSING [J].
BEARPARK, MJ ;
ROBB, MA ;
SCHLEGEL, HB .
CHEMICAL PHYSICS LETTERS, 1994, 223 (03) :269-274
[5]   The azulene S-1 state decays via a conical intersection: A CASSCF study with MMVB dynamics [J].
Bearpark, MJ ;
Bernardi, F ;
Clifford, S ;
Olivucci, M ;
Robb, MA ;
Smith, BR ;
Vreven, T .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (01) :169-175
[6]   MOLECULAR MECHANICS VALENCE-BOND METHODS FOR LARGE ACTIVE SPACES - APPLICATION TO CONJUGATED POLYCYCLIC-HYDROCARBONS [J].
BEARPARK, MJ ;
ROBB, MA ;
BERNARDI, F ;
OLIVUCCI, M .
CHEMICAL PHYSICS LETTERS, 1994, 217 (5-6) :513-519
[7]   ANOMALOUS LIGHT EMISSION OF AZULENE [J].
BEER, M ;
LONGUETHIGGINS, HC .
JOURNAL OF CHEMICAL PHYSICS, 1955, 23 (08) :1390-1391
[8]   SIMULATION OF MC-SCF RESULTS ON COVALENT ORGANIC MULTIBOND REACTIONS - MOLECULAR MECHANICS WITH VALENCE BOND (MM-VB) [J].
BERNARDI, F ;
OLIVUCCI, M ;
ROBB, MA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (05) :1606-1616
[9]   ELECTRONIC STATES OF PERIMETER PI SYSTEMS .4. ELECTRONIC SPECTRUM OF [18]ANNULENE [J].
BLATTMANN, HR ;
HEILBRONNER, E ;
WAGNIERE, G .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1968, 90 (18) :4786-+
[10]  
BOBROWICZ FW, 1977, MODERN THEORETICAL C, V3, pCH4