Charge transfer in ultrafast isomerization of acetylene ions

نویسندگان

چکیده

First-principle calculations are employed to investigate the ultrafast isomerization of acetylene cation and dication. We use time-dependent density functional theory together with Ehrenfest dynamics track coupled electron-nuclear dynamics. For both dication, we observe nonadiabatic behaviors during isomerization. find that charge transfer not only alters electronic structure through transitions, but also plays a key role in subsequent hydrogen migration. show transitions affect structural modification excited potential energy surface, facilitate creation channel increased negative facilitates proton movement. cation, timescale for $66\ifmmode\pm\else\textpm\fi{}4$ fs, which is consistent previous pump-probe experiments on-the-fly calculations. occur before identify similar proton. Moreover, formation vinylidene-like structures always accompanied by characteristic separation on carbon skeleton. These heuristics will be useful identifying tautomers motivating charge-transfer detection methods future experiments.

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ژورنال

عنوان ژورنال: Physical review

سال: 2022

ISSN: ['0556-2813', '1538-4497', '1089-490X']

DOI: https://doi.org/10.1103/physreva.106.033111