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Matrix Infrared Spectroscopy and a Theoretical Investigation of SUO and US 2
Author(s) -
Andrews Lester,
Wang Xuefeng,
Liang Binyong,
Ruipérez Fernando,
Infante Ivan,
Raw Adam D.,
Ibers James A.
Publication year - 2011
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201100561
Subject(s) - chemistry , bent molecular geometry , neon , molecule , argon , matrix isolation , ground state , infrared spectroscopy , spectroscopy , density functional theory , atomic physics , matrix (chemical analysis) , crystallography , computational chemistry , physics , organic chemistry , quantum mechanics , chromatography
Abstract US 2 and SUO molecules have been prepared by laser ablation of the solid materials and reaction of the elements during condensation in solid argon, which give the same absorptions as earlier U atom reactions with sulfur vapor and sulfur dioxide. The antisymmetric stretching mode of US 2 shifts from 438.7 cm –1 in solid argon to 442.3 cm –1 in solid neon, which shows that the same electronic state is trapped in both matrix environments. Density functional calculations find a bent ( 3 B 2 ) ground state for the US 2 molecule, and CASSCF/CASPT2 calculations reveal a multiconfigurational mixture of (5fφ) 1 (5fδ) 1 ‐type states, whereas the most stable state for UO 2 is a linear structure of the (5fφ)(7s) type. The bent triplet ground state SUO molecule exhibits similar multireference character with the U–O stretching mode at 857.1 cm –1 in solid argon. The linear SUO molecule computed at the CASPT2 level is only 2 kcal/mol above the bent structure. A detailed analysis of the bonding in US 2 and SUO is provided and compared to the better known UO 2 molecule.