An Infrared Spectroscopic and Density Functional Theoretical Investigation of the Reaction Products of Laser-Ablated Scandium and Titanium Atoms with Nitric Oxide

Abstract

Laser-ablated Sc and Ti atoms have been reacted with NO during condensation in excess argon. Matrix infrared spectra show that the major products are the side-bonded Sc[NO] species and the inserted NScO and NTiO molecules based on isotopic substitution (15N16O and 15N18O) and DFT calculations of isotopic frequencies, which provide a match for two modes in three isotopic modifications for each molecule. The NScO and NTiO molecules are nitride/oxides with M−O stretching modes only 46−88 cm-1 below the diatomic metal oxides but M−N stretching modes 314−442 cm-1 lower than the diatomic metal nitride molecules. The ScN, ScO and TiN, TiO molecules are observed as decomposition products. Evidence is also presented for the nitrosyls ScNO and TiNO, the Sc[NO]+ cation, and the NTiO- anion.