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• W2068470586 abstract "This paper attempts to give a theoretical interpretation of the anomalies observed in the spectra of the hydrogen-bonded centrosymmetric dimers. The analyzed effects were observed in the numerous recently published dimeric spectra and ascribed to a deviation from the dipole selection rules for the centrosymmetric dimers; they depend on activation of the forbidden transition in IR to the Ag excited state of the proton stretching vibrations in the hydrogen bonds. A vibronic model of interactions in the hydrogen bonds was assumed, which allowed one to derive a purely electronic matrix Hamiltonian of a dimer. It described mixing between the dimeric vibrational states, belonging to different irreducible representations of the Ci group. In our model two kinds of interactions, i.e., the vibronic coupling in the Herzberg-Teller approximation and proton vibration anharmonicity, played an essential role in the coupling mechanism and determined the shape of the Hamiltonian. The analysis of some Hamiltonian properties allowed one to conclude that in some cases the vibrational transition to the Ag state may be allowed for the dimers as a result of a modified Herzberg-Teller mechanism, originally established for the molecular electronic spectra to explain the vibrational spectral phenomena. The deviation from the selection rule is connected with a dynamic asymmetry of the electron charge distribution and with a dynamic asymmetry of the protonic positions in the Ag excited state of the proton vibrations. The model also predicts diminution of the forbidden transition intensity after replacing the H-atoms by the D-atoms in the dimeric hydrogen bonds." @default.
• W2068470586 created "2016-06-24" @default.
• W2068470586 creator A5089135677 @default.
• W2068470586 date "1989-05-01" @default.
• W2068470586 modified "2023-10-17" @default.
• W2068470586 title "On the vibrational transition selection rules for the centrosymmetric hydrogen-bonded dimeric systems" @default.
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• W2068470586 doi "https://doi.org/10.1016/0166-1280(89)85148-6" @default.
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