A multiconfigurational study of anion-radical and dianion of 1,3-dinitrobenzene

被引：17

作者：

Mikhailov, M. N. ^{[1
]}

Mendkovich, A. S. ^{[1
]}

Kuminsky, M. B. ^{[1
]}

Rusakov, A. I. ^{[2
]}

机构：

[1] Russian Acad Sci, ND Zelinskii Organ Chem Inst, Moscow 119991, Russia

[2] PG Demidov Yaroslavl State Univ, Yaroslavl 150000, Russia

来源：

JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM | 2007年 / 847卷 / 1-3期

关键词：

anion-radical; dianion; 1,3-dinitrobenzene; intramolecular electron transfer; CASSCF; MRMP2;

D O I：

10.1016/j.theochem.2007.09.006

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 CASSCF method was used to reveal the structure of anion-radical (AR) and dianion (DA) of 1,3-dinitrobenzene in ground and lowest excited states. The calculations indicate the presence of two asymmetric ((2)A") and one C-2v symmetric ((2)A(2)) structures of AR. The asymmetric AR-(2)A" structure is 4 kcal/mol more stable than the symmetric AR-(2)A(2) configuration. In contrast to AR, DA in the ground triplet (B-3(1)) and in the lowest singlet ((1)A(1)) states is characterized by the C-2v symmetric structure. The wavefunction of the singlet state is of biradical nature and the singlet triplet splitting for DA is equal to 2 kcal/mol. (c) 2007 Elsevier B.V. All rights reserved.

引用

页码：103 / 106

页数：4

共 23 条

[1] [Anonymous], RUSS CHEM REV
[2] Contemporary issues in electron transfer research
Barbara, PF
Meyer, TJ
Ratner, MA
[J]. JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (31) : 13148 - 13168
[3] Intramolecular dynamics of 1,2,3-trifluorobenzene radical anions as studied by OD ESR and quantum-chemical methods
Barlukova, MM
Beregovaya, IV
Vysotsky, VP
Shchegoleva, LN
Bagryansky, VA
Molin, YN
[J]. JOURNAL OF PHYSICAL CHEMISTRY A, 2005, 109 (19) : 4404 - 4409
[4] Factors controlling regioselectivity in the reduction of polynitroaromatics in aqueous solution
Barrows, SE
Cramer, CJ
Truhlar, DG
Elovitz, MS
Weber, EJ
[J]. ENVIRONMENTAL SCIENCE & TECHNOLOGY, 1996, 30 (10) : 3028 - 3038
[5] Theoretical study of the changes in the electronic structure of benzonitrile accompanying its conversion into a radical anion
Dimitrova, Y
[J]. JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM, 1996, 362 (01): : 23 - 27
[6] Gallardo I, 2001, CHEMPHYSCHEM, V2, P754, DOI 10.1002/1439-7641(20011217)2:12<754::AID-CPHC754>3.0.CO
[7] 2-U
[8] Evidence for a π dimer in the electrochemical reduction of 1,3,5-trinitrobenzene:: A reversible N2-fixation system
Gallardo, Iluminada
Guirado, Gonzalo
Marquet, Jordi
Vila, Neus
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (08) : 1321 - 1325
[9] Granovsky A.A., PC GAMESS VERSION 7
[10] REACTIONS OF CATHODIC DIMERIZATION IN NON-AQUEOUS MEDIA - CONSIDERATION IN TERMS OF THE THEORY OF MOLECULAR-ORBITAL PERTURBATIONS
GULTYAI, VP
MENDKOVICH, AS
[J]. JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1983, 145 (01): : 201 - 203

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