OMS, OM(η2-SO), and OM(η2-SO)(η2-O2S) Molecules (M = Ce, Th) with Chiral Structure: Matrix Infrared Spectra and Theoretical Calculations

Tengfei Huang; Qiang Wang; Wenjie Yu; Xuefeng Wang; Lester Andrews

doi:10.1021/acs.jpca.8b03731

OMS, OM(η²-SO), and OM(η²-SO)(η²-O₂S) Molecules (M = Ce, Th) with Chiral Structure: Matrix Infrared Spectra and Theoretical Calculations

J Phys Chem A. 2018 Jun 21;122(24):5391-5400. doi: 10.1021/acs.jpca.8b03731. Epub 2018 Jun 11.

Authors

Tengfei Huang¹, Qiang Wang^{1

2}, Wenjie Yu¹, Xuefeng Wang¹, Lester Andrews³

Affiliations

¹ School of Chemical Science and Engineering , Tongji University , Shanghai 200092 , P. R. China.
² State Key Laboratory of Coal Conversion, Institute of Coal Chemistry , Chinese Academy of Sciences , Taiyuan 030001 , P. R. China.
³ Department of Chemistry , University of Virginia , Charlottesville , Virginia 22904 , United States.

PMID: 29847728
DOI: 10.1021/acs.jpca.8b03731

Abstract

Infrared absorptions of the matrix isolated OMS, OM(η²-SO), and OM(η²-SO)(η²-O₂S) (M = Ce, Th) molecules were observed following reactions of laser-ablated Ce and Th metal atoms with SO₂ during condensation in excess argon and neon. Band assignments for the main vibrational modes were confirmed by appropriate ³⁴SO₂ and S¹⁸O₂ isotopic shifts. B3LYP, BPW91 density functional, and CASSCF/CASPT2 calculations were performed to characterize these new reaction products and to explore the admixture of f orbitals into the bonding giving stronger M≡O triple bonds. It is very interesting that both OM(η²-SO) and OM(η²-SO)(η²-O₂S) molecules show chiral structure.