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Fast estimation of the internal conversion rate constant in photophysical applications
Author(s) -
Rashid R. Valiev,
Rinat T. Nasibullin,
Victor N. Cherepanov,
A. E. Kurtсevich,
Dage Sundholm,
Theo Kurtén
Publication year - 2021
Publication title -
physical chemistry chemical physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.053
H-Index - 239
eISSN - 1463-9084
pISSN - 1463-9076
DOI - 10.1039/d1cp00257k
Subject(s) - adiabatic process , reaction rate constant , constant (computer programming) , internal conversion , matrix (chemical analysis) , coupling (piping) , thermodynamics , chemistry , physics , materials science , computer science , classical mechanics , kinetics , quantum mechanics , chromatography , metallurgy , spectral line , programming language
An efficient method for estimating non-adiabatic coupling matrix elements (NACME) and rate constants for internal conversion (k IC ) is presented. The method, based on Plotnikov's theory, requires only calculations of the electronic wave functions and the corresponding electronic excitation energies. Computationally expensive calculations of the derivatives of the electronic wave function with respect to the nuclear coordinates are avoided. When the main accepting modes of the electronic excitation energy are X-H vibrations, the present method can be used for estimating the efficiency of the energy transfer between donor and acceptor molecules. It can also be used in studies of the influence of hydrogen bonding or solvent effect on fluorescence quenching, in studies of vibronic effects of TADF (thermally activated delayed fluorescence) emitters, and for calculating k IC . Here, k IC and NACME are calculated for free-base porhyrin, magnesium porphyrin, azulene, naphthalene, pyrene and fluorenone interacting with a solvent molecule. Reverse k IC and NACME are further calculated for the T 1 → T 2 ransition of dibenzothiophene-S,S-dioxide (PTZ-DBTO2), which is used in TADF applications. Finally, we estimate the efficiency of the energy transfer between two large porphyrinoid dimers.

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