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Chiral Induction on the Ultrafast Event of Excited State Proton Transfer Can Probe Its Mechanism
Author(s) -
Ghosh Pratyush,
Das Aritra,
Sen Pratik
Publication year - 2019
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201903249
Subject(s) - excited state , proton , adiabatic process , chemistry , femtosecond , atomic physics , chemical physics , diabatic , quantum , vibronic coupling , quantum tunnelling , molecular physics , ultrafast laser spectroscopy , physics , quantum mechanics , laser
When protonic motion is explained as a purely quantum mechanical phenomenon, two extreme situations can be visualized as either the adiabatic or the nonadiabatic limit of proton transfer (PT). Strong orbital coupling between the donor and the acceptor pair in the proton transfer step drives PT mechanism in the adiabatic limit whereas in nonadiabatic limit PT predominantly occurs through tunneling. Here we proposed a unique way to experimentally observe the adiabaticity of PT by introducing chirality in the reaction coordinate of excited state proton transfer (ESPT). We successfully established the existence of prominent role of diastereomerism in the ESPT by both steady state and femtosecond time‐resolved transient absorption spectroscopic measurements in the adiabatic limit. The presented novel approach can overcome the limitations of only available experimental technique, i. e. kinetic isotope effect, to elucidate proton transfer mechanism.