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Modeling the heating and cooling of a chromophore after photoexcitation

Elizete Ventura, Silmar A. do Monte, Mariana T. do Casal, Max Pinheiro, Josene M. Toldo, Mario Barbatti

2022Physical Chemistry Chemical Physics11 citationsDOIOpen Access PDF

Abstract

nonadiabatic dynamics of cytosine, a prototypical chromophore undergoing ultrafast internal conversion, in three solvents-argon matrix, benzene, and water-spanning an extensive range of interactions. We implemented an analytical energy-transfer model to analyze these data and extract heating and cooling times. The model accounts for nonadiabatic effects, and excited- and ground-state energy transfer, and can analyze data from any dataset containing kinetic energy as a function of time. Cytosine heats up in the subpicosecond scale and cools down within 25, 4, and 1.3 ps in argon, benzene, and water, respectively. The time constants reveal that a significant fraction of the benzene and water heating occurs while cytosine is still electronically excited.

Topics & Concepts

ChromophorePhotoexcitationEnergy transferSolventChemical physicsMolecular dynamicsHeat transferChemistryThermodynamicsPhotochemistryMaterials scienceComputational chemistryAtomic physicsPhysicsExcited stateOrganic chemistrySpectroscopy and Quantum Chemical StudiesPhotochemistry and Electron Transfer StudiesAdvanced Fluorescence Microscopy Techniques
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