LIF spectrum for the localised S0 → S1(ππ*) excitation in the H-bonded anthranilic acid dimer: Symmetry breaking or coupling of vibrations.

Kolek, Przemysław; Andrzejak, Marcin; Uchacz, Tomasz; Goclon, Jakub; Pogocki, Dariusz; Kisała, Joanna; Bankiewicz, Barbara; Szlachcic, Paweł; Tulej, Marek (2024). LIF spectrum for the localised S0 → S1(ππ*) excitation in the H-bonded anthranilic acid dimer: Symmetry breaking or coupling of vibrations. Spectrochimica acta. Part A - molecular and biomolecular spectroscopy, 319(124491), p. 124491. Elsevier 10.1016/j.saa.2024.124491

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This study aims to investigate the impact of the π → π* excitation localised in one monomer on the equilibrium geometry and oscillations of the AA dimer. Several low-frequency vibrations appear in pairs in the LIF spectrum because oscillations involving intermolecular hydrogen bonds are coupled, generating approximately symmetric and antisymmetric combinations (especially the COOH rocking modes, LIF: 295 and 301 cm-1). Furthermore, quantitative evaluation based on the TDDFT(B3LYP) results indicates that a dozen among 90 intramolecular oscillations are strongly coupled. In contrast, most vibrations are decoupled or weakly coupled, since they involve remote parts of the monomers. This makes several single vibrations active in the LIF spectrum (including the bending mode of the NH···O intramolecular hydrogen bond associated the strongest vibronic band 442 cm-1), while the other in each pair remains inactive. The reason for decoupling of oscillations and symmetry breaking is that the π → π* electronic excitation is entirely localised within one of the monomers, which makes them no longer equivalent in terms of geometry and dynamics. Additionally, the excitation of one monomer induces strengthening and shortening by 6 pm of only one intermolecular hydrogen bond linking the carboxylic groups of both molecules. This causes the 1.7° in-plane distortion of the dimer and lowering of its symmetry to Cs group (from C2h for the S0 state). The distortion induces the activity of two low-frequency in-plane intermolecular vibrations, i.e. the geared oscillation (LIF: 58 cm-1) and the shearing motion (99 cm-1) of the monomers.

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