O–H vibrational motions promote sub-50 fs nonadiabatic dynamics in 3-hydroxypyran-4-one: interplay between internal conversion and ESIPT

Abstract

The OH out-of-plane bend vibration induces an extremely rapid S2 to S1 internal conversion in 3-hydroxypyran-4-one.

Modern Theoretical Approaches to Modeling the Excited-State Intramolecular Proton Transfer: An Overview

“…Both investigations led to similar conclusions on a critical role of a conical intersection between bright S and dark S states, of respective * and n * character, which was interpreted as the reason for observation of two ESIPT rate constants for these molecules in the experiment. Anand et al applied the same methodology to study ESIPT also in similar 3-hydroxyflavone [ 150 ] and 3-hydroxypyran-4-one [ 151 ] systems, confirming the important role of the S state in their photorelaxation. Finally, recent thorough work by Cao et al provided theoretical insights on ESIPT-driven mechanism and quantum dynamics of thermally activated delayed fluorescence in triquinolonobenzene [ 152 ], in which singlet-state ultrafast proton transfer occurs within a dense manifold of low-lying triplet states.…”

“…Looking toward future developments that would further strengthen the field, support from machine learning techniques should definitely be considered a promising direction for the QD efficiency enhancement, with first results already emerging [ 153 , 154 ], so as to improve the performance of other dynamic approaches [ 155 ]. Moreover, linking solvent-dependent optical properties with nonadiabatic ESIPT dynamics within the fully quantum framework could also provide powerful new tool to the existing set [ 151 ], opening new-level possibilities, e.g., for describing the competition between intra- and intermolecular excited-state proton transfer reactions on equal footing.…”

Lack of the ESIPT band of aromatic ortho-aminoaldehyde derivatives triggered by N–H vibration

“…Recently, Anand et al studied the dynamics of ESIPT reactions in 3-hydroxypyran-4-one, revealing that the O–H vibrational motion could promote sub-50 fs nonadiabatic dynamics. 31 Bisht et al studied the ESIPT reactions of salicylic acid (SA) monomer and dimer, and they found that the emission spectrum was dominated by progressions in the O–H stretch and in-plane distortion of the carboxylic group. 23 In this discussion, to elucidate the lack of ESIPT bands in o -aminoaldehyde derivatives, the N–H vibrational motion should be taken into account.…”

ESIPT in the pyrrol pyridine molecule: mechanism, timescale and yield revealed using dynamics simulations

“…Dynamics methods on the other hand allow the explicit simulation of the proton transfer reaction. Full quantum dynamics methods such as Multi-Configuration Time-Dependent Hartree (MCTDH) [39][40][41][42][43][44] and semi-classical approaches such as Ab Initio Multiple Spawning (AIMS) 45,46 and surface hopping (with decoherence correction) [47][48][49][50][51][52][53] have been applied to investigate ESIPT. The Nuclear Electronic Orbital (NEO) method, which allows the full quantum treatment of a restricted set of nuclei (usually hydrogen), is a promising alternative in that context.…”