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Issue 8, 2018
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Ultrafast intersystem crossing for nitrophenols: ab initio nonadiabatic molecular dynamics simulation

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Abstract

Ultrafast intersystem crossing mechanisms for two p- and m-nitrophenol groups (PNP and MNP) have been investigated using ab initio nonadiabatic molecular dynamics simulations at the 6SA-CASSCF level of theory. Trajectory surface hopping simulation has been performed within an intersystem crossing network constructed from two low-lying singlets (S0 and S1) and two low-lying triplets (T1 and T2). It is found that the dominant relaxation S1 → T2 pathway accounts for 65.4% (85.0%) of the quantum yield with a time constant of 13.4 fs (22 fs) and the S1 → T2 → S0 pathway accounts for 33.1% (13.5%) with a time constant of 275 fs (375 fs) for PNP (MNP). In comparison with the previously studied excited-state proton transfer process for ONP, the dominant relaxation S1 → T2 → T1 pathway accounts for 49.3% with a time constant of 40 fs and the S1 → T2 → T1 → S0 pathway accounts for 47.5% with a time constant of 300 fs. The relaxation mechanisms and electronic structures of the intersystem crossings are in close relation with the relative motion between the torsion motions of the nitro-group and the hydroxyl group. The present simulation provides new physical insight for understanding ultrafast photochemical intersystem crossing dynamics.

Graphical abstract: Ultrafast intersystem crossing for nitrophenols: ab initio nonadiabatic molecular dynamics simulation

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Publication details

The article was received on 24 Dec 2017, accepted on 23 Jan 2018 and first published on 23 Jan 2018


Article type: Paper
DOI: 10.1039/C7CP08601F
Citation: Phys. Chem. Chem. Phys., 2018,20, 5606-5616
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    Ultrafast intersystem crossing for nitrophenols: ab initio nonadiabatic molecular dynamics simulation

    C. Xu, F. L. Gu and C. Zhu, Phys. Chem. Chem. Phys., 2018, 20, 5606
    DOI: 10.1039/C7CP08601F

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