Knowledge Bank

Transition metal-nitrogen complexes of the form TM$\mathrm{<mrow\; data-mjx-texclass="ORD">+</mrow>}$(N$2$) (TM=V, Fe, Nb) are produced in a laser vaporization pulsed nozzle cluster source, size selected with a time-of-flight mass spectrometer and excited in the infrared with an infrared OPO/OPA. Infrared photodissociation occurs by elimination of whole N$2$ molecules and the photofragement yield versus wavelength produces IR resonance-enhanced photodissociation (REPD) spectra for the clusters. Vibrational bands seen in the 2100 - 2400 cm$\mathrm{<mrow\; data-mjx-texclass="ORD">-1</mrow>}$ region correspond to the N-N stretch but are shifted from those of free N$2$. Density functional theory calculations on the bond energeries, geometries and frequency shifts for the TM$\mathrm{<mrow\; data-mjx-texclass="ORD">+</mrow>}$(N$2$) are also discussed in regard to periodic trends.