Ultrafast nonadiabatic excited-state intramolecular proton transfer in 3-hydroxychromone: A surface hopping approach.

We employ the ab initio molecular dynamics within the surface hopping method to explore the excited-state intramolecular proton transfer taking place on the coupled "bright" S (ππ*) and "dark" S (nπ*) states of 3-hydroxychromone. The nonadiabatic population transfer between these states via an accessible conical intersection would open up multiple proton transfer pathways. Our findings reveal the keto tautomer formation via S on a timescale similar to the O-H in-plane vibrational period (<100 fs).

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

A theoretical study is used to explore the involvement of O-H vibrational motions in the S0 → S2 photoinduced dynamics of 3-hydroxypyran-4-one (3-HOX). Two transitions, S0 → S1 and S0 → S2, are attributed to the experimentally observed electronic absorption spectral features in the range of 3.5-5.

Excited-state intramolecular proton transfer driven by conical intersection in hydroxychromones.

Nonradiative decay pathways associated with vibronically coupled S (ππ*)-S (nπ*) potential energy surfaces of 3- and 5-hydroxychromones are investigated by employing the linear vibronic coupling approach. The presence of a conical intersection close to the Franck-Condon point is identified based on the critical examination of computed energetics and structural parameters of stationary points. We show that very minimal displacements of relevant atoms of intramolecular proton transfer geometry are adequate to drive the molecule toward the conical intersection nuclear configuration.

Nonadiabatic excited-state intramolecular proton transfer in 3-hydroxyflavone: S state involvement via multi-mode effect.

The excited-state intramolecular proton transfer process in 3-hydroxyflavone is investigated based on the computed structural parameters and energetics of stationary points of vibronically coupled S-S potential energy surfaces. A conical intersection close to the Franck-Condon point on S is identified. The minimum energy of the conical intersection is found to be near-degenerate with the equilibrium minimum of S.