%0 DATA
%A A., Marzouk
%A H., Bolvin
%A P., Reinhardt
%A L., Manceron
%A J. P., Perchard
%A B., Tremblay
%A M. E., Alikhani
%D 2014
%T A Combined
Experimental and Theoretical Study of the Ti_{2} + N_{2}O Reaction
%U https://acs.figshare.com/articles/A_Combined_Experimental_and_Theoretical_Study_of_the_Ti_sub_2_sub_N_sub_2_sub_O_Reaction/2329597
%R 10.1021/jp406479n.s001
%2 https://ndownloader.figshare.com/files/3967225
%K N 2O ReactionThe reactivity
%K vibrational transitions
%K metastable product OTi 2N
%K quantum chemical calculations
%K cm
%K CCSD
%K DFT
%K ab initio calculations
%X The reactivity of diatomic titanium
with nitrous oxide has been studied in solid neon. Two molecules with
the same Ti_{2}–N_{2}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^{–1}, the high frequency one
at 946 cm^{–1} 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 *C*_{s} 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_{2}–N_{2}O molecule, only observed after annealing, is easily converted
into the first one upon irradiation above 12 000 cm^{–1} and its kinetics of photoconversion allows vibrational transitions
to be identified. The strongest one located at 2123.4 cm^{–1} 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_{2}N_{2} and correctly account for the observed spectra of the
various isotopic varieties.