Reactions of Laser-Ablated Iron Atoms with N₂O, NO, and O₂ in Condensing Nitrogen. Infrared Spectra and Density Functional Calculations of Ternary Iron Nitride Oxide Molecules

Abstract

Reactions of laser-ablated Fe atoms with N 2 O, NO, and O 2 in excess N 2 during condensation at 10 K produced new absorptions with 15 N and 18 O shifts that are assigned to the new ternary iron nitride oxide molecules NFeO, NFeO 2 , and N 2 FeO. DFT calculations of structure and isotopic frequencies support these assignments.

Ab initio multireference singles and doubles configuration interaction study of the low‐energy states of iron mononitride

“…The four lowest lying states are dominated by single configurations. Our results agree with previous works on FeN [3][4][5][6][7], and support the attribution that the ground state is indeed the 2 D with the 4 P state only 0.06 eV higher in energy. All values in cm À1 .…”

“…In doing so, the spin-orbit components 4 P 5/2 and 4 P 3/2 lie 811 and 1223 cm À1 above the ground state and are tentatively assigned as states b and c. Symmetry analysis of the DF bands also indicated that states b and c should have a different symmetry from the ground state. It was suggested that state a should also be a spin-orbit component of 4 P, in spite of the fact that its vibrational progression does not appear in the same bands where b and c progressions do and that no theoretical level nearer the ground state was left to account for it (a low-lying 6 R þ state was discarded by symmetry reasons). When we include the same splitting estimates in our MR-SDCI results, we end up with spin-orbit components of the 4 P state 215, 627, 1039, and 1451 cm À1 above the 2 D 5/2 state.…”

“…In a previous infrared study, Andrews and coworkers [6] have carried out the reaction of laser ablated iron atoms with NO and N 2 O in excess N 2 carrier gas. Some bands of the IR spectrum were attributed to FeN, and the results of density functional theory (DFT) calculations were used to support their assignments.…”

Fixation of nitrogen in an electrospray mass spectrometer

“…Formation of [FeOH(H 2 O)] + would give an ion with a calculated m/z of 90.9481, and, indeed, this ion was experimentally observed at m/z 90.9483. Andrews and coworkers have studied the reactions of laser‐ablated iron atoms, establishing that iron and its oxides react with N 2 8–10. They reported the formation of the pyramidal iron dinitride oxide, [N 2 FeO], demonstrating that the observed and calculated infrared bands matched well.…”

“…They reported the formation of the pyramidal iron dinitride oxide, [N 2 FeO], demonstrating that the observed and calculated infrared bands matched well. They also documented that the FeN bond is relatively strong 9. Betley and Peters later showed that an iron nitride could be reduced to ammonia at room temperature 11…”