O–H vibrational motions promote sub-50 fs nonadiabatic dynamics in 3-hydroxypyran-4-one: interplay between internal conversion and ESIPT
Literature Information
Neethu Anand, Probal Nag, Ravi Kumar Kanaparthi, Sivaranjana Reddy Vennapusa
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 3.5–5.5 eV. We compute model potential energy surfaces of vibronically coupled S1 (nπ*) and S2 (ππ*) states with the aid of extensive electronic structure calculations. The S1–S2 conical intersection is characterized in the O–H bend and O–H stretch vibrational coordinate space. Quantum wavepacket dynamics simulations reveal an ultrafast S2 → S1 internal conversion decay, where about 90% of the S2 population disappears within the first 50 fs of the propagation time. The participation of O–H vibrational motions in the early events of nonadiabatic dynamics is analyzed based on the time evolution of nuclear densities on S2. We discuss the implications of these observations to provide fundamental insights into the nonadiabatic excited-state intramolecular proton transfer in 3-HOX and its derivatives.
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Source Journal
Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.











![N-[2,6-Di(9-anthryl)-4-oxido-8,9,10,11,12,13,14,15-octahydrodinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-yl]-1,1,1-trifluoromethanesulfonamide structure N-[2,6-Di(9-anthryl)-4-oxido-8,9,10,11,12,13,14,15-octahydrodinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-yl]-1,1,1-trifluoromethanesulfonamide structure](https://static.chemtradehub.com/structs/122/1227374-64-2-cdb5.webp)


