REACTIONS OF LASER-ABLATED CO AND NI ATOMS WITH NITROGEN-ATOMS AND MOLECULES - INFRARED-SPECTRA AND DFT CALCULATIONS OF METAL NITRIDE MOLECULAR-SPECIES AND COMPLEXES
L. Andrews et al., REACTIONS OF LASER-ABLATED CO AND NI ATOMS WITH NITROGEN-ATOMS AND MOLECULES - INFRARED-SPECTRA AND DFT CALCULATIONS OF METAL NITRIDE MOLECULAR-SPECIES AND COMPLEXES, The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 102(15), 1998, pp. 2561-2571
Laser-ablated Co and Ni atoms, co-deposited with pure nitrogen at 10 K
, gave a strong new 795.3 cm(-1) band with cobalt and a 838.8, 836.1 c
m(-1) isotopic doubler (2.5/1.0) with nickel, which exhibited 14/15 is
otopic ratios appropriate for the diatomic CoN and NiN molecules. In s
olid argon, CoN absorbs at 826.5 cm(-1) and gives way on annealing to
bands at 795.8 and 792.0 cm(-1), which are due to (NN)(x)CoN complexes
. Density functional theory (DFT) calculations predict quintet and qua
rter ground states for CoN and NiN, respectively, and frequencies in r
easonable agreement with the observed values. Evidence is also present
ed for the dimetal dinitrides, (CoN)(2) and (NiN)(2), with rhombus str
uctures and metal-metal bonding across the ring. DFT-based calculation
s and revised assignments are presented for NI-NN stretching modes in
the dinitrogen complexes.