Cryogenic Photoelectron Spectroscopic and Theoretical Study of the Electronic and Geometric Structures of Undercoordinated Osmium Chloride Anions OsCln– (n = 3–5)

Tang, Peng; Zhang, Jian; Li, Xueying; Yang, Fan; Zhao, Qixu; Ma, Junyang; Hu, Zhubin; Sun, Haitao; Wang, Xue-Bin; Sun, Zhenrong; Yang, Yan

doi:10.1021/acs.jpca.4c01713

Cryogenic Photoelectron Spectroscopic and Theoretical Study of the Electronic and Geometric Structures of Undercoordinated Osmium Chloride Anions OsCl_n^– (n = 3–5)

Journal Article · Fri Jul 05 00:00:00 EDT 2024 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.4c01713· OSTI ID:2475660

Tang, Peng ^[1]; Zhang, Jian ^[2]; Li, Xueying ^[1]; Yang, Fan ^[1]; Zhao, Qixu ^[1]; Ma, Junyang ^[1]; Hu, Zhubin ^[1]; ^[1]; ^[3]; Sun, Zhenrong ^[4]; ^[1]

East China Normal Univ. (ECNU), Shanghai (China)
Donghua University, Shanghai (China)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
East China Normal Univ. (ECNU), Shanghai (China); Shanxi Univ., Taiyuan (China)

A series of anionic transition metal halides OsCl_n^- (n=3–5) have been investigated using a newly developed, home-constructed, cryogenic anion cluster photoelectron spectroscopy. Here, the target anionic species are generated through collision-induced dissociation in a two-stage ion funnel. The measured vertical detachment energies (VDEs) are 3.48 eV, 4.54 eV, and 4.81 eV for n = 3, 4, and 5, respectively. Density functional theory calculations at the B3LYP-D3(BJ)//aug-cc-pVTZ (-pp) level predict the lowest energy structures of OsCl_n^- (n = 3–5) to be a quintet triangle, quartet square, and quintet square-based pyramid, respectively. The CCSD(T)-calculated VDEs and corresponding adiabatic detachment energies (ADEs) agree well with our experimental measurements. Analysis of the corresponding frontier molecular orbitals (FMOs) and charge density differences suggests that the d-orbitals of the transition metal Os play a primary role in the single-photon detachment processes, and the detached electrons originating from different molecular orbitals are distinguishable.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: National Natural Science Foundation of China (NSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 2475660

Report Number(s):: PNNL-SA--200114

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 28 Vol. 128; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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