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Investigation of Photochemical Paths by a Combined Theoretical and Experimental Approach

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Strategies and Applications in Quantum Chemistry

Part of the book series: Topics in Molecular Organization and Engineering ((MOOE,volume 14))

Conclusion

The aim of the present work was to show that, while awaiting the development of efficient quantum and statistical mechanical procedures able to provide qualitatively and quantitatively satisfactory descriptions of both static and dynamic aspects of photoreactions in condensed phase, at the present time some useful results can be obtained by combining traditional quantum-chemical calculations of potential energy surfaces with specially selected photophysical and photochemical measurements. This simple strategy consists in leading the theoretical description and the experimental analysis to a point where their direct comparison is freed from most arbitrariness factors. For example, with reference to photoreactions where bulky groups perform large amplitude motions combined with substantial changes in electronic distribution (like that reported in section 3), the work should go as far as to obtain kinetic parameters cleared of the solvent viscosity effects and compare them with those deducible from the calculated potential energy surfaces corrected for the solvation effects in a solvent of similar dielectric constant. Procedures of this type can serve a dual purpose: 1) to state to what extent the photoreaction mechanism and dynamics may be controlled by the polarity or the viscosity of the solvent, 2) to test the calculated intramolecular potential surfaces. As regards point 2) the reported study on the trans-cis photoisomerism of BMPC gave clear evidence for the soundness of the CS INDO method as well as the reasonableness of the model adopted to estimate the effects of the solvent polarity. On this basis, and the results of several other applications, we can assert that the CS INDO CI technique is a fairly effective and supple tool for dealing with the static (electronic) aspects of photoprocesses, especially those involving large conjugated molecules such as, for example, pigments and dyes having central roles in biological systems or technological devices.

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Author information

Authors and Affiliations

  1. Dipartimento di Chimica, Università di Modena, Via Campi 183, I-41100, Modena, Italy

    F. Momicchioli, I. Baraldi, A. Carnevali & G. Ponterini

Authors
  1. F. Momicchioli
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  2. I. Baraldi
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  3. A. Carnevali
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  4. G. Ponterini
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Editors and Affiliations

  1. Ecole Normale Supérieure & Observatoire de Paris, Paris, France

    Y. Ellinger

  2. Commissariat à l’Energie Atomique, Saclay, France

    M. Defranceschi

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© 1996 Kluwer Academic Publishers

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Momicchioli, F., Baraldi, I., Carnevali, A., Ponterini, G. (1996). Investigation of Photochemical Paths by a Combined Theoretical and Experimental Approach. In: Ellinger, Y., Defranceschi, M. (eds) Strategies and Applications in Quantum Chemistry. Topics in Molecular Organization and Engineering, vol 14. Springer, Dordrecht. https://doi.org/10.1007/0-306-46930-8_27

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  • DOI: https://doi.org/10.1007/0-306-46930-8_27

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-0-7923-3837-6

  • Online ISBN: 978-0-306-46930-5

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