A theoretical insight into excited-state decay and proton transfer of<i>p</i>-nitrophenylphenol in the gas phase and methanol solution

Tang, Xiu-Fang; Jia, Pei-Ke; Zhao, Yanying; Xue, Jingling; Cui, Ganglong; Xie, Binbin

doi:10.1039/d2cp02452g

Cited by 2 publications

(2 citation statements)

References 56 publications

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“…It is well-known that the DFT method can give a reasonable description of geometric structures in the ground state at a relatively low computational cost. , Therefore, the ground-state minimum structures of lutein, labeled as S 0 (1Ag – ), were first optimized with B3LYP functionals with 6-31G* and 6-31G ** basis sets. In addition, the cheaper semiempirical OM2/MRCI(20,20) method (see Figure ) and the more expensive multi-configurational CASSCF and RASSCF methods with different basis sets were also performed to locate the same ground-state minimum structure.…”

Section: Resultsmentioning

confidence: 99%

Understanding the Excited-State Relaxation Mechanisms of Xanthophyll Lutein by Multi-configurational Electronic Structure Calculations

Yin

Wang

Xue

et al. 2023

J. Chem. Inf. Model.

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The contradictory behaviors in light harvesting and non-photochemical quenching make xanthophyll lutein the most attractive functional molecule in photosynthesis. Despite several theoretical simulations on the spectral properties and excited-state dynamics, the atomic-level photophysical mechanisms need to be further studied and established, especially for an accurate description of geometric and electronic structures of conical intersections for the lowest several electronic states of lutein. In the present work, semiempirical OM2/MRCI and multi-configurational restricted active space self-consistent field methods were performed to optimize the minima and conical intersections in and between the 1Ag − , 2Ag − , 1Bu + , and 1Bu − states. Meanwhile, the relative energies were refined by MS-CASPT2(10,8)/6-31G*, which can reproduce correct electronic state properties as those in the spectroscopic experiments. Based on the above calculation results, we proposed a possible excitedstate relaxation mechanism for lutein from its initially populated 1Bu + state. Once excited to the optically bright 1Bu + state, the system will propagate along the key reaction coordinate, i.e., the stretching vibration of the conjugated carbon chain. During this period of time, the 1Bu − state will participate in and forms a resonance state between the 1Bu − and 1Bu + states. Later, the system will rapidly hop to the 2Ag − state via the 1Bu + /2Ag − conical intersection. Finally, the lutein molecule will survive in the 2Ag − state for a relatively long time before it internally converts to the ground state directly or via a twisted S 1 /S 0 conical intersection. Notably, though the photophysical picture may be very different in solvents and proteins, the current theoretical study proposed a promising calculation protocol and also provided many valuable mechanistic insights for lutein and similar carotenoids.

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Section: Resultsmentioning

confidence: 99%

Understanding the Excited-State Relaxation Mechanisms of Xanthophyll Lutein by Multi-configurational Electronic Structure Calculations

Yin

Wang

Xue

et al. 2023

J. Chem. Inf. Model.

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“…Because of the intramolecular charge transfer, the NO 2 group substitution in hydroxyaromatic compounds can increase the acidity of the OH group, particularly in the excited state after photo-excitation. According to reports for p -nitrophenylphenol 9,41,42 and 4-nitro-1-naphthol, 8 the enhanced acidity allows hydroxyaromatic compounds 43–45 to ESPT to some organic weak bases, such as t -butylamine (TBA) and alcohols. As a result, 8-hydroxy-5-nitroquinoline may favor an ESPT over 8-hydroxyquinoline.…”

Section: Introductionmentioning

confidence: 99%

Excited state proton transfer in the triplet state of 8-hydroxy-5-nitroquinoline: a transient absorption and time-resolved resonance Raman spectroscopic study

Wang

Zhang

Pan

et al. 2023

Phys. Chem. Chem. Phys.

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A theoretical insight into excited-state decay and proton transfer ofp-nitrophenylphenol in the gas phase and methanol solution

Abstract: The excited-state decay (ESD) and proton transfer (EPT) of p‑nitrophenylphenol (NO2-Bp-OH), especially in the triplet states, were not characterized with the high-level theoretical methods to date. Herein, the MS-CASPT2//CASSCF and...

Cited by 2 publications

References 56 publications

Understanding the Excited-State Relaxation Mechanisms of Xanthophyll Lutein by Multi-configurational Electronic Structure Calculations

Understanding the Excited-State Relaxation Mechanisms of Xanthophyll Lutein by Multi-configurational Electronic Structure Calculations

Excited state proton transfer in the triplet state of 8-hydroxy-5-nitroquinoline: a transient absorption and time-resolved resonance Raman spectroscopic study

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