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Tautomers of homophthalic anhydride in the ground and excited electronic states: analysis through energy, hardness and vibrational signatures

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Abstract

The keto-enol tautomerisation in homophthalic anhydride (HA) is investigated in the ground (S0) and excited (S1) electronic states. The keto form with a dicarbonyl structure is found to be the most stable form in S0 and enol form with a monocarbonyl structure in S1 indicating an excited state intramolecular proton transfer (ESIPT) process. The computed results show consistency with the change in basis sets and methods of calculations. Apart from the two tautomers, transition states are also identified. The barrier to interconversion is found to reduce substantially in S1. Internal reaction coordinate (IRC) calculations confirm the pathway of interconversion between the two forms in S0 and S1. The observed FT-IR spectra corroborate well with our computed spectra. The appearance of two strong lines around 1800 cm−1 confirms the lowest energy structure to be the keto tautomer with a dicarbonyl form in S0. Our computations corroborate well with the crystal structure data for an analogous molecule. Electron distribution in HOMO and LUMO indicate the excitation process as π → π* in nature. The qualitative chemical concepts like hardness and electrophilicity are calculated to estimate the stability of the tautomers. The energy and hardness profiles with the variation of IRC are opposite to each other, verifying the principle of maximum hardness.

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Funding

AC gratefully acknowledges the support received from University Grants Commission through a research project (F. No. 37-560/2009(SR)) for conducting this work. The authors also acknowledge the instrumental support from DST (Govt. of India) under departmental FIST programme of University of Burdwan (Grant No. SR/FST/PS-II-/2018/52(C)) and University Grants Commission (UGC) for departmental CAS (Grant No. F.530/20/CAS-II/2018(SAP-I)) scheme.

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  1. Department of Physics, The University of Burdwan, Golapbag Campus, Burdwan, West Bengal, 713104, India

    Goutam Dey & Abhijit Chakraborty

  2. Department of Physics, Darjeeling Government College, Hill Cart Road, Darjeeling, West Bengal, 734101, India

    Goutam Dey

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Dey, G., Chakraborty, A. Tautomers of homophthalic anhydride in the ground and excited electronic states: analysis through energy, hardness and vibrational signatures. J Mol Model 26, 173 (2020). https://doi.org/10.1007/s00894-020-04411-7

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