Preprint Article Version 1 Preserved in Portico This version is not peer-reviewed

Vibronic and Cationic Features of 2-Fluorobenzonitrile and 3-Fluorobenzonitrile Studied by REMPI and MATI Spectroscopy and Franck-Condon Simulations

Version 1 : Received: 26 May 2023 / Approved: 29 May 2023 / Online: 29 May 2023 (13:41:56 CEST)

A peer-reviewed article of this Preprint also exists.

Li, S.; Zhao, Y.; Jiao, Y.; Zhao, J.; Li, C.; Jia, S. Vibronic and Cationic Features of 2-Fluorobenzonitrile and 3-Fluorobenzonitrile Studied by REMPI and MATI Spectroscopy and Franck–Condon Simulations. Molecules 2023, 28, 4702. Li, S.; Zhao, Y.; Jiao, Y.; Zhao, J.; Li, C.; Jia, S. Vibronic and Cationic Features of 2-Fluorobenzonitrile and 3-Fluorobenzonitrile Studied by REMPI and MATI Spectroscopy and Franck–Condon Simulations. Molecules 2023, 28, 4702.

Abstract

The fluorinated organic compounds have superior physicochemical properties than general organic compounds due to the strong C-F single bond, and widely used in medicine, biology, pesticides, and materials science. In order to gain a deeper understanding of the physicochemical properties of fluorinated organic compounds, fluorinated aromatic compounds have been investigated by various spectroscopic techniques. 2-Fluorobenzonitrile and 3-fluorobenzonitrile are important fine chemical intermediates, and their excited state S1 and cationic ground state D0 vibrational features remain unknown. In this paper, we used two-color resonance two photon ionization (2-color REMPI) and mass analyzed threshold ionization (MATI) spectroscopy to study S1 and D0 states vibrational features of 2-fluorobenzonitrile and 3-fluorobenzonitrile. The precise excitation energy (band origin) and adiabatic ionization energy were determined to be 36028 2 cm-1 and 78650 5 cm-1 for 2-fluorobenzonitrile; and 35989 2 cm-1 and 78873 5 cm-1 for 3-fluorobenzonitrile, respectively. The density functional theory (DFT) at the levels of RB3LYP/aug-cc-pvtz, TD-B3LYP/aug-cc-pvtz, and UB3LYP/aug-cc-pvtz were used to calculate the stable structures and vibrational frequencies for the ground states S0, excited state S1, and cationic ground state D0, respectively. Franck-Condon spectral simulations for transitions of S1 S0 and D0 S1 were performed based on above DFT calculations. The theoretical and experimental results are in good agreement. The observed vibrational features in S1 and D0 states are assigned according to the simulated spectra and the comparison with structurally similar molecules. Several experimental findings and molecular features were discussed in detail.

Keywords

fluorobenzonitrile; vibronic spectroscopy; cationic spectroscopy; MATI; Franck-Condon simulation

Subject

Chemistry and Materials Science, Physical Chemistry

Comments (0)

We encourage comments and feedback from a broad range of readers. See criteria for comments and our Diversity statement.

Leave a public comment
Send a private comment to the author(s)
* All users must log in before leaving a comment
Views 0
Downloads 0
Comments 0
Metrics 0


×
Alerts
Notify me about updates to this article or when a peer-reviewed version is published.
We use cookies on our website to ensure you get the best experience.
Read more about our cookies here.