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UV excitations of halons

Abstract : In the present study, we examined the UV excitations of a newly introduced molecular set, Halons-9, composed of nine gaseous halon molecules. The performance of the density functional-based multi-reference configuration interaction method (DFT/MRCI) and time-dependent density functional theory with CAM-B3LYP functional (TD-CAM-B3LYP) in the computation of singlet and triplet excited states of this set was evaluated against coupled-cluster with singles and doubles (CCSD). Excited states up to the corresponding ionization limits, including both localized and delocalized excitations, have been benchmarked. TD-CAM-B3LYP significantly underestimates excitation energies of the higher mixed valence-Rydberg and Rydberg states, with computed mean absolute deviations from the equation of motion (EOM)-CCSD results 1.06 and 0.76 eV, respectively. DFT/MRCI gives a significantly better description of higher excited states, albeit still poor, compared to the TD-CAM-B3LYP. The mean absolute deviations of mixed valence-Rydberg and Rydberg states from the reference EOM-CCSD values are 0.66 and 0.47 eV, respectively. The performance of DFT/MRCI for description of strongly correlated states with valence-Rydberg mixing is still not satisfactory enough. On the other hand, oscillator strengths of most of singlet states obtained with both methods are close to the EOM-CCSD values. The largest deviations, occurring in the case of several high-lying multiconfigurational states, are of an order of magnitude.
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https://hal-amu.archives-ouvertes.fr/hal-01415841
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Submitted on : Tuesday, December 13, 2016 - 4:19:06 PM
Last modification on : Wednesday, November 6, 2019 - 9:16:02 AM

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Ljiljana Stojanović, Abdulrahman O. Alyoubi, Saadullah G. Aziz, Rifaat H. Hilal, Mario Barbatti. UV excitations of halons. Journal of Chemical Physics, American Institute of Physics, 2016, 145 (18), pp.184306. ⟨10.1063/1.4967170⟩. ⟨hal-01415841⟩

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