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Determination of the cationic conformational structure of tetrahydrothiophene by one-photon MATI spectroscopy and Franck-Condon fitting

Title
Determination of the cationic conformational structure of tetrahydrothiophene by one-photon MATI spectroscopy and Franck-Condon fitting
Authors
Lee, Yu RanKim, Hong LaeKwon, Chan Ho
Ewha Authors
이유란
SCOPUS Author ID
이유란scopus
Issue Date
2020
Journal Title
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
ISSN
1463-9076JCR Link

1463-9084JCR Link
Citation
PHYSICAL CHEMISTRY CHEMICAL PHYSICS vol. 22, no. 11, pp. 6184 - 6191
Publisher
ROYAL SOC CHEMISTRY
Indexed
SCIE; SCOPUS WOS
Document Type
Article
Abstract
The conformers of tetrahydrothiophene (THT) in the neutral (S-0) and cationic (D-0) ground states have attracted significant attention in terms of the conformational interconversion through pseudorotation. Herein, these conformers were explored by utilising one-photon mass-analysed threshold ionization (MATI) spectroscopy using the coherently tunable vacuum ultraviolet laser pulse generated by four-wave difference-frequency mixing in Kr medium, which allowed the acquisition of the vibrational spectrum of the corresponding cation. To identify the conformer corresponding to the measured MATI spectrum, the potential energy surfaces associated with pseudorotation in the S-0 and D-0 states were constructed at the B3LYP/cc-pVTZ level, where the twisted conformer with C-2 symmetry in both states lies at the global minimum, while the C-s and C-2v conformations were located at the saddle points. Although most of the peaks observed in the spectrum could be assigned as the ionic transitions between the twisted conformers (C-2 symmetry) in the S-0 and D-0 states, distinct nontotally symmetric modes could not be assigned to any allowed vibration. Hence, Franck-Condon fitting was applied for the vibrational assignments in the observed spectrum. This revealed that the cationic conformer had a bent-like twist conformation of C-1 symmetry instead of C-2 symmetry. Furthermore, the geometrical changes induced by the removal of an electron from the non-bonding orbital of the sulfur atom gave prominent overtones and combination bands of the ring out-of-plane modes associated with pseudorotation as well as the stretching of 2C-1S-3C in the ring.
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DOI
10.1039/d0cp00073f
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자연과학대학 > 물리학전공 > Journal papers
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