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Chemical Physics Letters
Volume 404, Issues 1-3, 7 March 2005, Pages 150-155
 
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doi:10.1016/j.cplett.2005.01.036    How to Cite or Link Using DOI (Opens New Window)
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, Corresponding Author Contact Information, E-mail The Corresponding Author

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 2A22B1 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.

Article Outline

1. Introduction
2. Methods of calculation
3. Results and discussion
4. Concluding remarks
Acknowledgements
References




 
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