American Chemical Society
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Quantitatively Adequate Calculations of the H‑Chelate Ring Distortion upon the S0 → S1(ππ*) Excitation in Internally H‑Bonded o‑Anthranilic Acid: CC2 Coupled-Cluster versus TDDFT

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journal contribution
posted on 2018-07-02, 00:00 authored by Przemysław Kolek, Marcin Andrzejak, Rafał Hakalla, Wojciech Szajna
The S0 → S1(π → π*) excitation in o-aminobenzoic acid causes strengthening of the N–H···O intramolecular hydrogen bond. The interplay of the hydrogen bond shortening, the hydrogen atom dislocation along the hydrogen bond, and the skeletal relaxation is investigated. These effects often cause the appearance of dual fluorescence from the π-conjugated internally H-bonded molecules, which is traditionally interpreted as the evidence of the excited-state intramolecular proton transfer process: ESPIT. Hence, their quantitative modeling is an important but demanding task for computational photochemistry. Extensive calculations using CC2 method (the perturbative approximation to CCSD coupled-cluster) and TDDFT­(B3LYP) were performed with the series of (aug)-cc-pVXZ­(X = D,T,Q) basis sets. CC2 predicts remarkable shortening of the O···H distance by 0.273 Å accompanied by the skeleton relaxation that involves considerable distortions of valence angles of the amino group (up to 7.3°) and within the benzene ring (up to 5°). Additionally, moderate changes (<0.046 Å) of the bond alternation in the π-electronic system and the hydrogen atom dislocation along the hydrogen bond (0.043 Å) are predicted. The CC2 method yields 90% of the magnitude of the experimentally based geometry changes, estimated in the earlier studies via Franck–Condon fit to the LIF spectra, while the TDDFT results approach only 65% of the experimental values.