Bond Dissociation Dynamics And Thermodynamics Of Nio⁺ And Nis⁺

Lockwood, Schuyler P

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https://hdl.handle.net/2142/111507 Copy

Description

Title

Bond Dissociation Dynamics And Thermodynamics Of Nio⁺ And Nis⁺

Author(s)

Lockwood, Schuyler P

Contributor(s)

Metz, Ricardo B.

Issue Date

2021-06-25

Keyword(s)

Photodissociation and photochemistry

Abstract

Transition metal oxide and sulfide cations activate C-H bonds in the gas phase; several oxide cations activate methane and convert it to methanol at room temperature. However, a lack of experimental data on the energetics and dynamics of these species makes it difficult to model their reactions with hydrocarbons. We perform photofragment ion imaging experiments and ab initio calculations to determine the bond strength and photodissociation dynamics of the nickel oxide (NiO$^{+}$) and nickel sulfide (NiS$^{+}$) cations. NiO$^{+}$ photodissociates broadly from 25000 to 32000 \wn via an excited $^{4}$$\Sigma$$^{-}$ state, exclusively forming Ni$^{+}$ ($^{4}$F) + O ($^{3}$P) products at photolysis energies above ~29000 \wn. Photofragment images of NiO$^{+}$ show resolved Ni$^{+}$ ($^{4}$F$_{9/2}$) + O ($^{3}$P) and Ni$^{+}$ ($^{4}$F$_{7/2}$) + O ($^{3}$P) product spin-orbit channels; the lower energy (J = 9/2) channel dominates at photolysis energies of ~29000 to ~32000 \wn. The photofragment spectrum of NiS$^{+}$ from 19800 to 23200 \wn is highly structured, with ~12 distinct vibronic peaks each containing underlying spin-orbit structure. Photofragment images of NiS$^{+}$ collected over this region show slight parallel anisotropy, suggesting the highly structured photodissociation spectrum of NiS$^{+}$ in this region predominantly arises from a $\Delta$$\Lambda$ = 0 transition. Above 21600 \wn, the Ni$^{+}$ ($^{2}$D$_{5/2}$) + S ($^{3}$P) and Ni$^{+}$ ($^{2}$D$_{3/2}$) + S ($^{3}$P) product spin-orbit channels compete, with a branching ratio of ~0.5. Temperature-dependent spectra suggest peaks below 20150 \wn result from hot bands. Images taken slightly above the dissociation threshold (20600 \wn) show resolved S ($^{3}$P$_{2}$) and S ($^{3}$P$_{1}$) spin-orbit channels. Our D$_{0}$ measurements for NiO$^{+}$ (D$_{0}$ = 244.6 +/- 2.4 kJ/mol) and NiS$^{+}$ (D$_{0}$ = 240.3 +/- 1.4 kJ/mol) are more precise and closer to each other than previously reported values.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

Text

Language

eng

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http://hdl.handle.net/2142/111507

DOI

10.15278/isms.2021.FJ05

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