TY - JOUR

T1 - Modeling of cationic and excited states of γ-substituted boron difluoride acetylacetonates

AU - Tikhonov, Sergey A.

AU - Samoilov, Ilya S.

AU - Svistunova, Irina V.

AU - Chekh, Alexander S.

AU - Krauklis, Irina V.

AU - Vovna, Vitaliy I.

PY - 2019/12/5

Y1 - 2019/12/5

N2 - Modeling of cationic and excited states of boron difluoride acetylacetonate and eight of its γ-substituted derivatives was carried out using the methods of outer-valence Green's functions (OVGF), algebraic-diagrammatic construction for the polarization propagator of the second order (ADC(2)), coupled clusters with single and double excitations (EOM-CCSD), and time-dependent density functional theory (TDDFT/CAMB3LYP). Comparison of the calculated data with the absorption spectra made it possible to determine the influence of functional groups on the energies of electronic transitions and the nature of the absorption spectrum bands. Addition of the substituent SPh causes a decrease in the energy gap between the levels of the highest occupied and lowest vacant molecular orbitals, which determine the bathochromic shift of the long-wavelength band in the absorption spectrum relative to the other studied complexes. In the complexes containing Cl, Br, SCN, SEt, SPh and OS(O)2Ph groups in the γ-position, it was found that the highest occupied molecular orbitals are localized mainly on the substituents, and the lowest vacant molecular orbital corresponds to the chelate orbital π4, which determines the presence of transitions with charge transfer. It was shown that the calculated energies of excited states according to the ADC(2) method, in comparison with EOM-CCSD and TDDFT/CAMB3LYP, can be correlated with maxima of the experimental absorption spectra for the lowest average shift (0.27 eV).

AB - Modeling of cationic and excited states of boron difluoride acetylacetonate and eight of its γ-substituted derivatives was carried out using the methods of outer-valence Green's functions (OVGF), algebraic-diagrammatic construction for the polarization propagator of the second order (ADC(2)), coupled clusters with single and double excitations (EOM-CCSD), and time-dependent density functional theory (TDDFT/CAMB3LYP). Comparison of the calculated data with the absorption spectra made it possible to determine the influence of functional groups on the energies of electronic transitions and the nature of the absorption spectrum bands. Addition of the substituent SPh causes a decrease in the energy gap between the levels of the highest occupied and lowest vacant molecular orbitals, which determine the bathochromic shift of the long-wavelength band in the absorption spectrum relative to the other studied complexes. In the complexes containing Cl, Br, SCN, SEt, SPh and OS(O)2Ph groups in the γ-position, it was found that the highest occupied molecular orbitals are localized mainly on the substituents, and the lowest vacant molecular orbital corresponds to the chelate orbital π4, which determines the presence of transitions with charge transfer. It was shown that the calculated energies of excited states according to the ADC(2) method, in comparison with EOM-CCSD and TDDFT/CAMB3LYP, can be correlated with maxima of the experimental absorption spectra for the lowest average shift (0.27 eV).

KW - Algebraic-diagrammatic construction (ADC) method

KW - Boron difluoride β-diketonates

KW - Electronic structure

KW - Outer-valence Green's function (OVGF) method

KW - Photoelectron spectroscopy

KW - Polarization propagator

KW - Boron difluoride beta-diketonates

KW - PHOTOELECTRON-SPECTRA

KW - CRYSTAL-STRUCTURE

KW - OPTICAL-PROPERTIES

KW - ABSORPTION-SPECTRA

KW - LIQUID-CRYSTAL

KW - BETA-DIKETONATE COMPLEXES

KW - EXCITATION-ENERGIES

KW - BASIS-SETS

KW - ELECTRONIC-STRUCTURE

KW - TD-DFT

UR - http://www.scopus.com/inward/record.url?scp=85069002871&partnerID=8YFLogxK

UR - https://app.dimensions.ai/details/publication/pub.1117940188?subset_publication_citations=pub.1021125718

UR - http://www.mendeley.com/research/modeling-cationic-excited-states-%CE%B3substituted-boron-difluoride-acetylacetonates

U2 - 10.1016/j.molstruc.2019.07.030

DO - 10.1016/j.molstruc.2019.07.030

M3 - Article

AN - SCOPUS:85069002871

VL - 1197

SP - 108

EP - 116

JO - Journal of Molecular Structure

JF - Journal of Molecular Structure

SN - 0022-2860

ER -