Vibronic and Cationic Features of 2-Fluorobenzonitrile and 3-Fluorobenzonitrile Studied by REMPI and MATI Spectroscopy and Franck–Condon Simulations
Fluorinated organic compounds have superior physicochemical properties than general organic compounds due to the strong C-F single bond; they are widely used in medicine, biology, pesticides, and materials science. In order to gain a deeper understanding of the physicochemical properties of fluorina...
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MDPI AG
2023-06-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/12/4702 |
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| author | Shuxian Li Yan Zhao Yuechun Jiao Jianming Zhao Changyong Li Suotang Jia |
| author_facet | Shuxian Li Yan Zhao Yuechun Jiao Jianming Zhao Changyong Li Suotang Jia |
| author_sort | Shuxian Li |
| collection | DOAJ |
| description | Fluorinated organic compounds have superior physicochemical properties than general organic compounds due to the strong C-F single bond; they are 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 S<sub>1</sub> and cationic ground state D<sub>0</sub> 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 S<sub>1</sub> and D<sub>0</sub> state vibrational features of 2-fluorobenzonitrile and 3-fluorobenzonitrile. The precise excitation energy (band origin) and adiabatic ionization energy were determined to be 36,028 ± 2 cm<sup>−1</sup> and 78,650 ± 5 cm<sup>−1</sup> for 2-fluorobenzonitrile and 35,989 ± 2 cm<sup>−1</sup> and 78,873 ± 5 cm<sup>−1</sup> 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 state S<sub>0</sub>, excited state S<sub>1</sub>, and cationic ground state D<sub>0</sub>, respectively. Franck–Condon spectral simulations for transitions of S<sub>1</sub> ← S<sub>0</sub> and D<sub>0</sub> ← S<sub>1</sub> were performed based on the above DFT calculations. The theoretical and experimental results were in good agreement. The observed vibrational features in S<sub>1</sub> and D<sub>0</sub> states were assigned according to the simulated spectra and the comparison with structurally similar molecules. Several experimental findings and molecular features were discussed in detail. |
| first_indexed | 2024-03-11T02:05:53Z |
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| language | English |
| last_indexed | 2024-03-11T02:05:53Z |
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| spelling | doaj.art-03d68e1f3896440bbe1a77778f2bb9152023-11-18T11:49:11ZengMDPI AGMolecules1420-30492023-06-012812470210.3390/molecules28124702Vibronic and Cationic Features of 2-Fluorobenzonitrile and 3-Fluorobenzonitrile Studied by REMPI and MATI Spectroscopy and Franck–Condon SimulationsShuxian Li0Yan Zhao1Yuechun Jiao2Jianming Zhao3Changyong Li4Suotang Jia5State Key Laboratory of Quantum Optics and Quantum Optic Devices, Institute of Laser Spectroscopy, Shanxi University, Taiyuan 030006, ChinaDepartment of Physics and Electronics Engineering, Jinzhong University, Jinzhong 030619, ChinaState Key Laboratory of Quantum Optics and Quantum Optic Devices, Institute of Laser Spectroscopy, Shanxi University, Taiyuan 030006, ChinaState Key Laboratory of Quantum Optics and Quantum Optic Devices, Institute of Laser Spectroscopy, Shanxi University, Taiyuan 030006, ChinaState Key Laboratory of Quantum Optics and Quantum Optic Devices, Institute of Laser Spectroscopy, Shanxi University, Taiyuan 030006, ChinaState Key Laboratory of Quantum Optics and Quantum Optic Devices, Institute of Laser Spectroscopy, Shanxi University, Taiyuan 030006, ChinaFluorinated organic compounds have superior physicochemical properties than general organic compounds due to the strong C-F single bond; they are 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 S<sub>1</sub> and cationic ground state D<sub>0</sub> 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 S<sub>1</sub> and D<sub>0</sub> state vibrational features of 2-fluorobenzonitrile and 3-fluorobenzonitrile. The precise excitation energy (band origin) and adiabatic ionization energy were determined to be 36,028 ± 2 cm<sup>−1</sup> and 78,650 ± 5 cm<sup>−1</sup> for 2-fluorobenzonitrile and 35,989 ± 2 cm<sup>−1</sup> and 78,873 ± 5 cm<sup>−1</sup> 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 state S<sub>0</sub>, excited state S<sub>1</sub>, and cationic ground state D<sub>0</sub>, respectively. Franck–Condon spectral simulations for transitions of S<sub>1</sub> ← S<sub>0</sub> and D<sub>0</sub> ← S<sub>1</sub> were performed based on the above DFT calculations. The theoretical and experimental results were in good agreement. The observed vibrational features in S<sub>1</sub> and D<sub>0</sub> states were assigned according to the simulated spectra and the comparison with structurally similar molecules. Several experimental findings and molecular features were discussed in detail.https://www.mdpi.com/1420-3049/28/12/4702fluorobenzonitrilevibronic spectroscopycationic spectroscopyMATIFranck–Condon simulation |
| spellingShingle | Shuxian Li Yan Zhao Yuechun Jiao Jianming Zhao Changyong Li Suotang Jia Vibronic and Cationic Features of 2-Fluorobenzonitrile and 3-Fluorobenzonitrile Studied by REMPI and MATI Spectroscopy and Franck–Condon Simulations Molecules fluorobenzonitrile vibronic spectroscopy cationic spectroscopy MATI Franck–Condon simulation |
| title | Vibronic and Cationic Features of 2-Fluorobenzonitrile and 3-Fluorobenzonitrile Studied by REMPI and MATI Spectroscopy and Franck–Condon Simulations |
| title_full | Vibronic and Cationic Features of 2-Fluorobenzonitrile and 3-Fluorobenzonitrile Studied by REMPI and MATI Spectroscopy and Franck–Condon Simulations |
| title_fullStr | Vibronic and Cationic Features of 2-Fluorobenzonitrile and 3-Fluorobenzonitrile Studied by REMPI and MATI Spectroscopy and Franck–Condon Simulations |
| title_full_unstemmed | Vibronic and Cationic Features of 2-Fluorobenzonitrile and 3-Fluorobenzonitrile Studied by REMPI and MATI Spectroscopy and Franck–Condon Simulations |
| title_short | Vibronic and Cationic Features of 2-Fluorobenzonitrile and 3-Fluorobenzonitrile Studied by REMPI and MATI Spectroscopy and Franck–Condon Simulations |
| title_sort | vibronic and cationic features of 2 fluorobenzonitrile and 3 fluorobenzonitrile studied by rempi and mati spectroscopy and franck condon simulations |
| topic | fluorobenzonitrile vibronic spectroscopy cationic spectroscopy MATI Franck–Condon simulation |
| url | https://www.mdpi.com/1420-3049/28/12/4702 |
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