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

Molecules ◽  
2021 ◽  
Vol 26 (17) ◽  
pp. 5140 ◽  
Author(s):  
Joanna Jankowska ◽  
Andrzej L. Sobolewski
Keyword(s):  
Excited State ◽  
Proton Transfer ◽  
Quantum Dynamics ◽  
Intramolecular Proton Transfer ◽  
Experimental Investigations ◽  
Chemical Methods ◽  
Theoretical Approaches ◽  
Quantum Chemical Methods ◽  
Process Studies ◽  
Different Levels

The excited-state intramolecular proton transfer (ESIPT) phenomenon is nowadays widely acknowledged to play a crucial role in many photobiological and photochemical processes. It is an extremely fast transformation, often taking place at sub-100 fs timescales. While its experimental characterization can be highly challenging, a rich manifold of theoretical approaches at different levels is nowadays available to support and guide experimental investigations. In this perspective, we summarize the state-of-the-art quantum-chemical methods, as well as molecular- and quantum-dynamics tools successfully applied in ESIPT process studies, focusing on a critical comparison of their specific properties.

Quantum Dynamics of the Excited-State Intramolecular Proton Transfer in 2-(2′-Hydroxyphenyl)benzothiazole

2009 ◽  
Vol 49 (2) ◽  
pp. 187-197 ◽  
Author(s):  
Justin Kim ◽  
Yinghua Wu ◽  
Jean-Luc Brédas ◽  
Victor S. Batista
Keyword(s):  
Excited State ◽  
Proton Transfer ◽  
Quantum Dynamics ◽  
Intramolecular Proton Transfer

scholarly journals Nonadiabatic quantum dynamics of the coherent excited state intramolecular proton transfer of 10-hydroxybenzo[h]quinoline

2021 ◽  
Author(s):  
David Picconi
Keyword(s):  
Excited State ◽  
Proton Transfer ◽  
Quantum Dynamics ◽  
Density Functional ◽  
Active Role ◽  
High Energy ◽  
Spectroscopic Studies ◽  
Intramolecular Proton Transfer ◽  
Time Resolved ◽  
Proton Transfer Reactions

The photoinduced nonadiabatic dynamics of the enol-keto isomerization of 10-hydroxybenzo[h]quinoline (HBQ) are studied computationally using high dimensional quantum dynamics. The simulations are based on a diabatic vibronic coupling Hamiltonian, which includes the two lowest ππ* excited states and a nπ* state, which has high energy in the Franck-Condon zone, but significantly stabilizes upon excited state intramolecular proton transfer. A procedure, applicable to large classes of excited state proton transfer reactions, is presented to parametrize this model using potential energies, forces and force constants, which, in this case, are obtained by time-dependent density functional theory. The wave packet calculations predict a time scale of 10-15 fs for the photoreaction, and reproduce the time constants and the coherent oscillations observed in time-resolved spectroscopic studies performed on HBQ. In contrast to the interpretation given to the most recent experiments, it is found that the reaction initiated by 1ππ* ← S0 photoexcitation proceeds essentially on a single potential energy surface, and the observed coherences bear signatures of Duschinsky mode-mixing along the reaction path. The dynamics after the 2ππ* ← S0 excitation are instead nonadiabatic, and the nπ* state plays a major role in the relaxation process. The simulations suggest a mainly active role of the proton in the isomerization, rather than a passive migration assisted by the vibrations of the benzoquinoline backbone.

scholarly journals Nonadiabatic quantum dynamics of the coherent excited state intramolecular proton transfer of 10-hydroxybenzo[h]quinoline

2021 ◽  
Author(s):  
David Picconi
Keyword(s):  
Excited State ◽  
Proton Transfer ◽  
Quantum Dynamics ◽  
Density Functional ◽  
Active Role ◽  
High Energy ◽  
Spectroscopic Studies ◽  
Intramolecular Proton Transfer ◽  
Time Resolved ◽  
Proton Transfer Reactions

Abstract The photoinduced nonadiabatic dynamics of the enol-keto isomerization of 10-hydroxybenzo[h]quinoline (HBQ) are studied computationally using high-dimensional quantum dynamics. The simulations are based on a diabatic vibronic coupling Hamiltonian, which includes the two lowest $$\pi \pi ^*$$ π π ∗ excited states and a $$n\pi ^*$$ n π ∗ state, which has high energy in the Franck–Condon zone, but significantly stabilizes upon excited state intramolecular proton transfer. A procedure, applicable to large classes of excited state proton transfer reactions, is presented to parametrize this model using potential energies, forces and force constants, which, in this case, are obtained by time-dependent density functional theory. The wave packet calculations predict a time scale of 10–15 fs for the photoreaction, and reproduce the time constants and the coherent oscillations observed in time-resolved spectroscopic studies performed on HBQ. In contrast to the interpretation given to the most recent experiments, it is found that the reaction initiated by $$1\pi \pi ^* \longleftarrow S_0$$ 1 π π ∗ ⟵ S 0 photoexcitation proceeds essentially on a single potential energy surface, and the observed coherences bear signatures of Duschinsky mode-mixing along the reaction path. The dynamics after the $$2\pi \pi ^* \longleftarrow S_0$$ 2 π π ∗ ⟵ S 0 excitation are instead nonadiabatic, and the $$n\pi ^*$$ n π ∗ state plays a major role in the relaxation process. The simulations suggest a mainly active role of the proton in the isomerization, rather than a passive migration assisted by the vibrations of the benzoquinoline backbone. Graphic Abstract

scholarly journals An enhanced sampling QM/AMOEBA approach: The case of the excited state intramolecular proton transfer in solvated 3-hydroxyflavone

2021 ◽  
Vol 154 (18) ◽  
pp. 184107
Author(s):  
Michele Nottoli ◽  
Mattia Bondanza ◽  
Filippo Lipparini ◽  
Benedetta Mennucci
Keyword(s):  
Excited State ◽  
Proton Transfer ◽  
Intramolecular Proton Transfer ◽  
Enhanced Sampling

scholarly journals The development of aryl-substituted 2-phenylimidazo[1,2-a]pyridines (PIP) with various colors of excited-state intramolecular proton transfer (ESIPT) luminescence in the solid state

2016 ◽  
Vol 4 (16) ◽  
pp. 3599-3606 ◽  
Author(s):  
Toshiki Mutai ◽  
Tatsuya Ohkawa ◽  
Hideaki Shono ◽  
Koji Araki
Keyword(s):  
Excited State ◽  
Solid State ◽  
Proton Transfer ◽  
Intramolecular Proton Transfer ◽  
Aryl Group ◽  
Red Emission ◽  
Wide Range

The color of ESIPT luminescence of HPIP is tuned in a wide range by the introduction of aryl group(s), and thus a series of PIPs showing blue to red emission is realized.

ChemInform Abstract: EXCITED-STATE INTRAMOLECULAR PROTON TRANSFER AND VIBRATIONAL RELAXATION IN 2-(2-HYDROXYPHENYL)BENZOTHIAZOLE

1983 ◽  
Vol 14 (28) ◽  
Author(s):  
K. DING ◽  
S. J. COURTNEY ◽  
A. J. G. STRANDJORD ◽  
S. FLOM ◽  
D. M. FRIEDRICH ◽  
...  
Keyword(s):  
Excited State ◽  
Proton Transfer ◽  
Vibrational Relaxation ◽  
Intramolecular Proton Transfer
Sign in / Sign up

Export Citation Format

Share Document