Electronic Excited States and UV–Vis Absorption Spectra of the Dihydropyrene/Cyclophanediene Photochromic Couple: a Theoretical Investigation - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of Physical Chemistry A Année : 2020

Electronic Excited States and UV–Vis Absorption Spectra of the Dihydropyrene/Cyclophanediene Photochromic Couple: a Theoretical Investigation

Résumé

The dihydropyrene (DHP) / cyclophanediene (CPD) is a fascinating photoswitchable organic system displaying negative photochromism. Upon irradiation in the visible region, the colored DHP can be converted to its open-ring CPD colorless isomer, which can be converted back to DHP by UV light. DHP and CPD thus possess very different absorption spectra whose absorption bands have never been assigned in detail so far. In this work, we characterize the vertical electronic transitions of the first six and seven excited states of DHP and CPD, respectively, aiming for a realistic comparison with experiment. We used state-of-the-art electronic structure methods (e.g., CASPT2, NEVPT2, XMCQDPT2, ADC(3)) capable of describing differential electron correlation. Vertical transition energies were also computed with time-dependent density functional theory (TD-DFT) and compared to these accurate methods. After the reliability of TD-DFT was validated for the main optical transitions, this efficient method was used to simulate the absorption spectra of DHP and CPD in the framework of the Franck-Condon Herzberg-Teller (FCHT) approximation and also using the nuclear ensemble (NE) approach. Overall, for both methods, 2 the simulated absorption spectra reproduce nicely the main spectral features of the DHP and CPD isomers, that is, the main four absorption bands of increasing intensity of DHP and the absorption rise below 300 nm for CPD.
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Dates et versions

hal-02534418 , version 1 (15-06-2020)

Identifiants

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Rudraditya Sarkar, Marie-Catherine Heitz, Guy Royal, Martial Boggio-Pasqua. Electronic Excited States and UV–Vis Absorption Spectra of the Dihydropyrene/Cyclophanediene Photochromic Couple: a Theoretical Investigation. Journal of Physical Chemistry A, 2020, 124 (8), pp.1567-1579. ⟨10.1021/acs.jpca.9b11262⟩. ⟨hal-02534418⟩
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