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Determination of the highest occupied molecular orbital and cationic structure of 2-chloropyridine by one-photon VUV-MATI spectroscopy and Franck-Condon fitting

Title
Determination of the highest occupied molecular orbital and cationic structure of 2-chloropyridine by one-photon VUV-MATI spectroscopy and Franck-Condon fitting
Authors
Lee, Yu RanChoi, NayoungKwon, 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. 36, pp. 20858 - 20866
Publisher
ROYAL SOC CHEMISTRY
Indexed
SCIE; SCOPUS WOS scopus
Document Type
Article
Abstract
2-Chloropyridine (2-CP) has received significant attention, owing to the effect of the substitution of a halogen in pyridine on the highest occupied molecular orbital (HOMO). To elucidate the substitution effect of the chlorine atom on the HOMO of pyridine, we obtained one-photon vacuum ultraviolet mass-analysed threshold ionization (VUV-MATI) spectra of 2-CP having(35)Cl or(37)Cl to analyse the isotope effect on the vibrational mode. Based on the 0-0 band in the MATI spectrum of 2-CP having(35)Cl, the adiabatic ionization energy was determined to be 9.4743 +/- 0.0005 eV (76 415 +/- 4 cm(-1)) with a similar value for(37)Cl, which is much lower but more accurate than the vertical value of 9.63 eV determined by photoelectron spectroscopy. Subsequently, the MATI spectrum, which was affected by the geometrical change with respect to the neutral geometry upon ionization, could be analysed by Franck-Condon fitting and spectral correlation between the two isotopomers. Notably, we observed the appearance of the out-of-plane ring bending modes resulting from ring distortion, unlike in pyridine. Furthermore, natural bond orbital analysis led to the conclusion that the warped structure withC(1)symmetry of cationic 2-CP is induced by the electron removal from the HOMO consisting of the pi orbital in the pyridine ring, which is stabilized by hyperconjugation with the lone-pair p orbitals of a nitrogen and chlorine atom.
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DOI
10.1039/d0cp03365k
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자연과학대학 > 물리학전공 > Journal papers
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