doi:10.1016/j.cplett.2005.01.036
Copyright © 2005 Elsevier B.V. All rights reserved.
Quantum chemical study of the electronic structure of the 1-methylene-3,5-didehydrobenzene triradical (C7H5)
Hue Minh Thi Nguyena, b, Tran Thanh Hueb, Jozef Peetersa and Minh Tho Nguyena,
, 
aDepartment of Chemistry, University of Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium
bFaculty of Chemistry, University of Education, Hanoi, Vietnam
Received 2 December 2004;
revised 31 December 2004.
Available online 11 February 2005.
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Abstract
We investigated the electronic structure of 1-methylene-3,5-didehydrobenzene triradical (MDB, C7H5) containing a σ1σ1 biradical benzene ring coupled with an exocyclic π1 CH2. MS-CASPT2(9,9)/ANO-L calculations reveal that MDB exhibits a low-spin doublet 2B1 (2Π) ground state, followed by an open-shell doublet 2A2 state with a 2A2–2B1 gap of 17 ± 3 kcal mol−1. The energy ordering of MDB is (kcal mol−1): X2B1 (0) < A2A2 (17) < a4A2 (20) < B2B2 (39) < b4A1 (59) < C2A1 (61) < c4B1 (75) < d4B2 (79). The doublet states are lower in energy than the quartets, violating Hund’s rule, due to a coupling of the two unpaired σ-electrons transforming the triradical into a radical.
Scheme 1. Distribution of three electrons in three orbitals.
Scheme 2. Some typical hydrocarbon triradicals.
Fig. 1. Shape of four highest-lying orbitals of the MDB triradical (C7H5) whose variable occupancy determines its electronic states.
Table 1.
Selected geometrical parameters of the MDB triradical obtained from CASSCF (9/9)/ANO-L calculations in eight lower-lying doublet and quartet statesa
a The parameters are defined as follows:

.
Table 2.
Energies calculated results using the CASSCF(9,9), CASPT2 and MS-CASPT2 method with the ANO-L basis set for MDB in eight lower lying electronic states
a 2 Stands for a doubly-occupied orbital, u and d correspond to singly-occupied α-spin and β-spin electrons, respectively.
b Zero-point energies (ZPE) were obtained from CASSCF(9,9)/ANO-L computations, without scaling.
c Values are corrected for ZPEs.