A combined photoelectron-imaging spectroscopic and theoretical investigation on the electronic structure of the VO2H anion. Issue 31 (24th May 2021)

• Record Type: Journal Article
• Authors: Wang, Yongtian; Han, Changcai; Hong, Jing; Fei, Zejie; Dong, Changwu; Liu, Hongtao; Xiong, Xiaogen
• Is Part Of: RSC advances. Volume 11:Issue 31(2021)
• Page Start: 18729
• Page End: 18736
• Publication Date: 2021-05-24
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/d1ra03173b
• Languages: English
• ISSNs: 2046-2069

Abstract

Abstract : The PES of VO2 H − was detected at 814 nm. The electronic configuration of anionic and neutral of VO2 H is 4 A′′ and 3 A′′, respectively. The electron was detached from the s-type 17a′ MO of the anionic ground state of VO2 H. Abstract : The electronic structure and vibrational spectrum of the VO2 H anion are explored by combining photoelectron imaging spectroscopy and density functional theoretical (DFT) calculations. The electron affinity (EA) of VO2 H is determined to be 1.304 ± 0.030 eV from the vibrationally resolved photoelectron spectrum acquired at 1.52 eV (814 nm). The anisotropy parameter ( β ) for the EA defined peak is measured to be 1.63 ± 0.10, indicating that it is the 17a′ (4s orbital of the vanadium atom) electron attachment leading to the formation of the ground state of the VO2 H anion. The vibrational fundamentals ν 1, ν 3, ν 4 and ν 5 are obtained for the neutral ground state. Experimental assignments are confirmed by energies from electronic structure calculations and Franck–Condon (FC) spectral simulations. These simulations support assigning the anion ground state as the results obtained from the B3LYP method. In addition, the molecular orbitals and bonding involved in the anionic VO2 H cluster are also examined based on the present theoretical calculations.