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Title: Experimental and theoretical studies of the structural and electronic properties of vanadium–benzene sandwich clusters and their anions: V{sub n}Bz{sub n}{sup 0/−} (n = 1–5) and V{sub n}Bz{sub n−1}{sup 0/−} (n = 2–5)

One end open V{sub n}Bz{sub n}{sup −} (n = 1–5; Bz = benzene) and both ends open V{sub n}Bz{sub n−1}{sup −} (n = 2–5) vanadium–benzene cluster anions were studied using anion photoelectron spectroscopy and density functional calculations. The smaller (n ≤ 3) V{sub n}Bz{sub n} and V{sub n}Bz{sub n−1} clusters and corresponding anions were found to have structural isomers, whereas full-sandwiched V{sub n}Bz{sub n+1} clusters preferred to form multiple-decker sandwich structures. Several isomeric V{sub 2}Bz{sub 2} structures were identified theoretically and the anion photoelectron spectra of V{sub 2}Bz{sub 2}{sup 0/−} were explained well by the coexistence of two isomeric structures: (1) a V{sub 2}-core structure sandwiched between benzene molecules and (2) an alternating sandwich structure with the spin state strongly dependent on the structure. The adiabatic electron affinity of both V{sub n}Bz{sub n} and V{sub n}Bz{sub n−1} was found to increase with the cluster size at larger sizes (n = 4 or 5) and approaches to that of V{sub n}Bz{sub n+1}. The evolution of the structural and electronic properties of V{sub n}Bz{sub m} and V{sub n}Bz{sub m}{sup −} (m = n and n − 1) with size is discussed in comparison with V{sub n}Bz{sub n+1} and V{sub n}Bz{sub n+1}{sup −}.
Authors:
 [1] ;  [1] ;  [2] ;  [1] ;  [2] ;  [3]
  1. Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522 (Japan)
  2. (Japan)
  3. (KiPAS), Keio University, 3-14-1, Hiyoshi, Kohoku-ku, Yokohama 223-8522 (Japan)
Publication Date:
OSTI Identifier:
22413267
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 21; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AFFINITY; ANIONS; BENZENE; COMPARATIVE EVALUATIONS; DENSITY FUNCTIONAL METHOD; ISOMERS; MOLECULES; PHOTOELECTRON SPECTROSCOPY; SPIN; VANADIUM