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Excited state distribution function for probing Herzberg–Teller vibronic coupling using linear optical response theory: Application to glassy pheophytin a
Author(s) -
Toutounji Mohamad
Publication year - 2021
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.26724
Subject(s) - excited state , anharmonicity , transition dipole moment , dipole , coupling (piping) , vibronic coupling , distribution function , function (biology) , chemistry , physics , molecular physics , computational chemistry , atomic physics , quantum mechanics , materials science , metallurgy , evolutionary biology , biology
The goal of the present work is to develop an excited‐state distribution function that can be used to calculate electronic transition dipole moment time correlation functions at a considerably low computational cost. An additional merit of the distribution function is its capability to probe the Hertzberg–Teller vibronic coupling effect in terms of the previously reported Condon correlation functions in the literature without having to start from the equilibrium density operator to probe spectral non‐Condon effects, thereby exploring Hertzberg–Teller vibronic coupling by building on the Condon regime. It is easily extendable to anharmonic systems. Model calculations are reported to show the high degree of accuracy and computational efficiency of the presented approach. Application to a photosynthetic system such as pheophytin a in triethylamine is provided.