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Theoretical study of the excited-state reaction paths of the OH and NH dissociation processes in barbituric acid

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Abstract

We studied the OH and NH dissociation mechanisms of eight tautomers of barbituric acid via excited states. The theoretical research was performed at the TD DFT level of theory (B3LYP). It was found that all mechanisms pass through the repulsive 1πσ* excited state whose excited-state reaction paths showed conical intersections S0–S1. Some OH dissociation mechanisms showed barrierless 1πσ* reaction paths which indicate an ultrafast relaxation of the 1πσ* excited states to the ground state. The study of the NH dissociation mechanisms revealed that almost all 1πσ* reaction paths show low energy barriers and minima before the conical intersections S0–S1.

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Acknowledgments

We thank the scientific research fund of the University of Plovdiv for the financial support of the calculations (project NI-11-HF007/2011).

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Authors and Affiliations

  1. Department of Physical Chemistry, University of Plovdiv, Tzar Assen 24 Str., Plovdiv, Bulgaria

    Vassil B. Delchev & Iva P. Ivanova

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  1. Vassil B. Delchev
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  2. Iva P. Ivanova
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Correspondence to Vassil B. Delchev.

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Delchev, V.B., Ivanova, I.P. Theoretical study of the excited-state reaction paths of the OH and NH dissociation processes in barbituric acid. Monatsh Chem 143, 1141–1150 (2012). https://doi.org/10.1007/s00706-012-0766-9

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  • DOI: https://doi.org/10.1007/s00706-012-0766-9

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