title: Experimental and theoretical studies of the structural and electronic properties of vanadium-benzene sandwich clusters and their anions: V(n)Bz(n)(0/-) (n = 1-5) and V(n)Bz(n-1)(0/-) (n = 2-5).
abstract: One end open V(n)Bz(n)(-) (n = 1-5; Bz = benzene) and both ends open V(n)Bz(n-1)(-) (n = 2-5) vanadium-benzene cluster anions were studied using anion photoelectron spectroscopy and density functional calculations. The smaller (n ≤ 3) V(n)Bz(n) and V(n)Bz(n-1) clusters and corresponding anions were found to have structural isomers, whereas full-sandwiched V(n)Bz(n+1) clusters preferred to form multiple-decker sandwich structures. Several isomeric V2Bz2 structures were identified theoretically and the anion photoelectron spectra of V2Bz2(0/-) were explained well by the coexistence of two isomeric structures: (1) a V2-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(n)Bz(n) and V(n)Bz(n-1) was found to increase with the cluster size at larger sizes (n = 4 or 5) and approaches to that of V(n)Bz(n+1). The evolution of the structural and electronic properties of V(n)Bz(m) and V(n)Bz(m)(-) (m = n and n - 1) with size is discussed in comparison with V(n)Bz(n+1) and V(n)Bz(n+1)(-).
authors.affiliation: Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan.
authors.forename: Tsugunosuke
authors.initials: T
authors.lastname: Masubuchi
authors.affiliation: Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan.
authors.forename: Takeshi
authors.initials: T
authors.lastname: Iwasa
authors.affiliation: Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan.
authors.forename: Atsushi
authors.initials: A
authors.lastname: Nakajima