Difluorodiazirine (CF2N2): A comparative quantum mechanical study of the first triplet and first singlet excited states

Autor(es)

Terrabuio, Luiz Alberto ^{[1, 2]} ; Andrade Haiduke, Roberto Luiz ^[2] ; Matta, Cherif F. ^{[3, 1, 4]}

Afiliação do(s) autor(es)

^[1] Mt St Vincent Univ, Dept Chem & Phys, Halifax, NS B3M 2J6 - Canada

^[2] Univ Sao Paulo, Inst Quim Sao Carlos, Dept Quim & Fis Mol, Ave Trabalhador Sao Carlense, BR-13560970 Sao Carlos, SP - Brazil

^[3] St Marys Univ, Halifax, NS B3H 3C3 - Canada

^[4] Dalhousie Univ, Halifax, NS B3H 4J3 - Canada

• Tipo de documento: Artigo Científico
• Fonte: Chemical Physics Letters; v. 655, p. 96-102, JUL 1 2016.
• Citações Web of Science: 5

Resumo

3,3'-Difluorodiazirine is a precursor of difluorocarbene radical (:CF2) which is used in organic synthesis and photo affinity labelling. This molecule possesses no dipole moment in the ground electronic state (S-0) but has a significant dipole moment (of magnitude similar to 0.97 D) in both its first (triplet, T-1) and second (singlet S-1) excited states. These equal dipole moments are shown to originate from widely differing atomic polarization and inter-atomic charge transfer terms (defined by the Quantum Theory of Atoms in Molecules (QTAIM)). The calculated vertical/adiabatic excitation energies for the T-1 and S-1 states are 2.81/2.63 and 3.99/3.78 eV, respectively. Geometries, vibrational frequencies, atomic charges and spin populations, and the localization-delocalization matrices (LDMs) (Matta, J. Comput. Chem. 35 (2014) 1165) of the excited states are compared with those of the ground state. All calculations have been conducted at the (U) QCISD/aug-cc-pVTZ level of theory. (C) 2016 Elsevier B.V. All rights reserved. (AU)

• Processo FAPESP: 10/18743-1 - Uso de multipolos da teoria quântica de átomos em moléculas e estudos cinéticos em sistemas encontrados no meio interestelar
• Beneficiário: Roberto Luiz Andrade Haiduke
• Modalidade de apoio: Auxílio à Pesquisa - Regular
• Processo FAPESP: 14/23714-1 - Cálculos relativísticos de estrutura eletrônica para avaliação de novos conjuntos de funções de base sem prolapso variacional
• Beneficiário: Roberto Luiz Andrade Haiduke
• Modalidade de apoio: Auxílio à Pesquisa - Regular