A Combined Theoretical and Experimental Study of the Reaction Products of Laser-Ablated Thorium Atoms with CO: First Identification of the CThO, CThO-, OThCCO, OTh(eta(3)-CCO), and Th(CO)(n) (n=1-6) Molecules

October 8, 2001

Journal Article

A Combined Theoretical and Experimental Study of the Reaction Products of Laser-Ablated Thorium Atoms with CO: First Identification of the CThO, CThO-, OThCCO, OTh(eta(3)-CCO), and Th(CO)(n) (n=1-6) Molecules

Abstract

Laser-ablated thorium atoms have been reacted with CO molecules during condensation in excess neon. Absorptions at 617.7 and 812.2 cm-1 are assigned to Th-C and Th-O stretching vibrations of the CThO molecule. Absorptions at 2048.6, 1353.6, and 822.5 cm-1 are assigned to the OThCCO molecule, which is formed by CO addition to CThO and photochemical rearrangement of Th(CO)2. The OThCCO molecule undergoes further photoinduced rearrangement to OTh(Eta3-CCO), which is characterized by C-C, C-O, and Th-O stretching vibrations at 1810.8, 1139.2, and 831.6 cm-1. The Th(CO)n (n ) 1-6) complexes are formed on deposition or on annealing. Evidence is also presented for the CThO- and Th(CO)2- anions, which are formed by electron capture of neutral molecules. Relativistic density functional theory (DFT) calculations of the geometry structures, vibrational frequencies, and infrared intensities strongly support the experimental assignments.

Revised: November 25, 2003 | Published: October 8, 2001

Citation

Li J., B.E. Bursten, and M. Zhou. 2001. A Combined Theoretical and Experimental Study of the Reaction Products of Laser-Ablated Thorium Atoms with CO: First Identification of the CThO, CThO-, OThCCO, OTh(eta(3)-CCO), and Th(CO)(n) (n=1-6) Molecules. Inorganic Chemistry 40, no. 21:5448-5460.