Marzouk, A.
Bolvin, H.
Reinhardt, P.
Manceron, L.
Perchard, J. P.
Tremblay, B.
Alikhani, M. E.
A Combined
Experimental and Theoretical Study of the Ti<sub>2</sub> + N<sub>2</sub>O Reaction
The reactivity of diatomic titanium
with nitrous oxide has been studied in solid neon. Two molecules with
the same Ti<sub>2</sub>–N<sub>2</sub>O stoichiometry are identified
from concentration, temperature, and irradiation effects. The more
stable one is characterized by five fundamental vibrational transitions
located below 1000 cm<sup>–1</sup>, the high frequency one
at 946 cm<sup>–1</sup> corresponding to a pure TiO stretching
mode. Its structure, a rhombus OTiNTiN with the extra O atom fixed
on one Ti, is confirmed by quantum chemical calculations, at the CCSD(T)
level, which predict a <i>C<sub>s</sub></i> structure in
the singlet state with a Ti–O bond length close to 1.66 Å,
two nonequivalent Ti–N distances close to 1.94 and 1.75 Å,
and a OTiTi angle of 119.2°. The second Ti<sub>2</sub>–N<sub>2</sub>O molecule, only observed after annealing, is easily converted
into the first one upon irradiation above 12 000 cm<sup>–1</sup> and its kinetics of photoconversion allows vibrational transitions
to be identified. The strongest one located at 2123.4 cm<sup>–1</sup> characterizes an N–N stretching mode. Corresponding ab initio
calculations complete this picture with details on the electronic
structure and allow us to identify a most adequate density functional
to describe the spectroscopic properties of the studied species in
a simpler broken-symmetry open-shell DFT context. The theoretical
results predict the existence of a metastable product OTi<sub>2</sub>N<sub>2</sub> and correctly account for the observed spectra of the
various isotopic varieties.
N 2O ReactionThe reactivity;vibrational transitions;metastable product OTi 2N;quantum chemical calculations;cm;CCSD;DFT;ab initio calculations
2014-01-23
https://acs.figshare.com/articles/A_Combined_Experimental_and_Theoretical_Study_of_the_Ti_sub_2_sub_N_sub_2_sub_O_Reaction/2329597

10.1021/jp406479n.s001