title: Structures and chemical bonding of B3O3 (-/0) and B3O3H(-/0): A combined photoelectron spectroscopy and first-principles theory study.
abstract: We present a combined photoelectron spectroscopy and first-principles theory study on the structural and electronic properties and chemical bonding of B3O3 (-/0) and B3O3H(-/0) clusters. The concerted experimental and theoretical data show that the global-minimum structures of B3O3 and B3O3H neutrals are very different from those of their anionic counterparts. The B3O3 (-) anion is characterized to possess a V-shaped OB-B-BO chain with overall C2 v symmetry (1A), in which the central B atom interacts with two equivalent boronyl (B≡O) terminals via B-B single bonds as well as with one O atom via a B=O double bond. The B3O3H(-) anion has a Cs (2A) structure, containing an asymmetric OB-B-OBO zig-zag chain and a terminal H atom interacting with the central B atom. In contrast, the C2 v (1a) global minimum of B3O3 neutral contains a rhombic B2O2 ring with one B atom bonded to a BO terminal and that of neutral B3O3H (2a) is also of C2 v symmetry, which is readily constructed from C2 v (1a) by attaching a H atom to the opposite side of the BO group. The H atom in B3O3H(-/0) (2A and 2a) prefers to interact terminally with a B atom, rather than with O. Chemical bonding analyses reveal a three-center four-electron (3c-4e) π hyperbond in the B3O3H(-) (2A) cluster and a four-center four-electron (4c-4e) π bond (that is, the so-called o-bond) in B3O3 (1a) and B3O3H (2a) neutral clusters.
authors.affiliation: Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
authors.forename: Li-Juan
authors.initials: LJ
authors.lastname: Zhao
authors.affiliation: Nanocluster Laboratory, Institute of Molecular Science, Shanxi University, Taiyuan 030006, China.
authors.forename: Wen-Juan
authors.initials: WJ
authors.lastname: Tian
authors.affiliation: Nanocluster Laboratory, Institute of Molecular Science, Shanxi University, Taiyuan 030006, China.
authors.forename: Ting
authors.initials: T
authors.lastname: Ou
authors.affiliation: Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
authors.forename: Hong-Guang
authors.initials: HG
authors.lastname: Xu
authors.affiliation: Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
authors.forename: Gang
authors.initials: G
authors.lastname: Feng
authors.affiliation: Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
authors.forename: Xi-Ling
authors.initials: XL
authors.lastname: Xu
authors.affiliation: Nanocluster Laboratory, Institute of Molecular Science, Shanxi University, Taiyuan 030006, China.
authors.forename: Hua-Jin
authors.initials: HJ
authors.lastname: Zhai
authors.affiliation: Nanocluster Laboratory, Institute of Molecular Science, Shanxi University, Taiyuan 030006, China.
authors.forename: Si-Dian
authors.initials: SD
authors.lastname: Li
authors.affiliation: Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
authors.forename: Wei-Jun
authors.initials: WJ
authors.lastname: Zheng