V3: Structure and vibrations from density functional theory, Franck–Condon factors, and the pulsed-field ionization zero-electron-kinetic energy spectrum

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DOIResolve DOI: http://doi.org/10.1063/1.1337859
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TypeArticle
Journal titleThe Journal Of Chemical Physics
Volume114
Issue9
Pages40364044; # of pages: 9
Subjectdensity functional theory; Franck-Condon factors; molecular configurations; photoionisation; positive ions; vanadium; vibrational states
AbstractDensity functional calculations of neutral and cationic vanadium trimers are presented. The all-electron calculations employed a gradient-corrected exchange-correlation functional and a newly developed vanadium basis set optimized for gradient-corrected density functional calculations. For both neutral and charged systems, different isomers were studied in order to determine the lowest energy structures. A vibrational analysis was performed in order to characterize these isomers. We found an equilateral triangle 2A<sub>1</sub><sup>[prime]</sup> ground state for V3 and an equilateral triangle 3A<sub>2</sub><sup>[prime]</sup> ground state for V<sub>3</sub><sup>+</sup>. The experimental pulsed-field ionization zero-electron-kinetic energy spectrum was simulated by calculating multidimensional Franck�Condon factors, using the geometries and harmonic frequencies of the calculated minima of V3 and V<sub>3</sub><sup>+</sup>. The excellent agreement between the experimental and theoretical spectra allows the unequivocal determination of the ground state structure of V3. This work provides a final answer to the controversy in the literature about the ground state structure of V3 and yields deeper insight into the electronic structure of the neutral and cationic systems.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada; NRC Steacie Institute for Molecular Sciences
Peer reviewedNo
NPARC number12327419
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Record identifier137b452a-04d8-4864-9081-05151a6d86fd
Record created2009-09-10
Record modified2016-05-09
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