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Difluorodiazirine (CF2N2): a quantum mechanical study of the electron density and of the electrostatic potential in the ground and excited electronic states

Texto completo
Terrabuio, Luiz Alberto [1, 2] ; Andrade Haiduke, Roberto Luiz [2] ; Matta, Cherif F. [3, 1, 4]
Número total de Autores: 3
Afiliação do(s) autor(es):
[1] Mt St Vincent Univ, Dept Chem & Phys, Halifax, NS B3M 2J6 - Canada
[2] Univ Sao Paulo, Dept Quim & Fis Mol, Inst Quim Sao Carlos, Ave Trabalhador Sao Carlense, 400 CP 780, BR-13560970 Sao Carlos, SP - Brazil
[3] Dalhousie Univ, Dept Chem, Halifax, NS B3H 4J3 - Canada
[4] St Marys Univ, Dept Chem, Halifax, NS B3H 3C3 - Canada
Número total de Afiliações: 4
Tipo de documento: Artigo Científico
Fonte: THEORETICAL CHEMISTRY ACCOUNTS; v. 135, n. 3 FEB 24 2016.
Citações Web of Science: 4

The difluorocarbene radical (:CF2), used in organic synthesis and in photoaffinity labeling, can be generated by the pyrolytic or photolytic decomposition of 3,3-difluorodiazirine (CF2N2, DFD). DFD possesses no dipole moment in the ground electronic state S-0 but has an experimental dipole of 1.5 +/- 0.2 debye (D) in its first singlet excited state S-1. These observations have been ascribed to the shift in electron population between orbitals (Frenking et al. in J Comp Chem 28: 117-126, 2007). An alternative real-space explanation is presented, which shows that the vanishing dipole moment in S-0 results from a balance between a charge transfer contribution due to the flow of charge between atoms and an atomic polarization term due to the non-sphericity of atoms in molecules. This balance is altered in S-1. This orbital-free description is shown to be consistent with an incipient dissociation of DFD to :CF2 and N-2 upon excitation. The Laplacian of the electron density and the molecular electrostatic potential exhibit significant reorganization on excitation, mirroring one another, with consequential changes in chemical reactivity. Conforming to Hund's rule, the lowest excited state is a triplet state (T-1), and the next level, the one examined in this work, is the first singlet excited state (S-1) with vertical excitation energies of 2.81 and 3.99 eV, respectively. The calculated dipole moment magnitudes (in D) are 0.05 (S-0), 0.973 (T-1), and 0.969 (S-1) all pointing their negative end toward the nitrogens. The maximal average lifetime of S-1 (in absence of non-radiative de- excitation) is ca. 30 ps, sufficient for its slowest vibrational normal mode to complete 400 oscillations. From a comparison of Hartree-Fock, MP2, QCISD, CCSD, and TD-DFT/B3LYP calculations with experiment (all using an aug-cc-pVTZ basis set), for both the ground and excited states of DFD, the method of choice appears to be QCISD, the one used in this work. (AU)

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
Linha de fomento: Auxílio à Pesquisa - Regular
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
Linha de fomento: Auxílio à Pesquisa - Regular