Spin-forbidden cΣ1+3←XΣ+1 band system of YF

Nagarajan, Ramya; Morse, Michael D.

doi:10.1063/1.2714525

Cited by 4 publications

(1 citation statement)

References 23 publications

(22 reference statements)

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“…We consider the chemiluminescent emission characterizing 16 reactions of the group 3 metals Sc, Y, and La and their dimers with F 2 , ClF, and Cl 2 as well as SF 6 ; Sc with Br 2 and ICl; Y with Br 2 and IBr; and Sc 2 and Y 2 with Cl and Br atoms. The available spectroscopic data from experiments ,,,,− ,− and calculations ,,− ,− ,− ,− are given in Tables – .…”

Section: Resultsmentioning

confidence: 99%

Observation of Selectively Populated Monohalide Excited States from the Reactions of Group 3 Metal (Sc, Y, and La) Monomers and Dimers with Halogen-Containing Molecules

et al. 2022

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The chemiluminescent reactions of the group 3 metals Sc and Y with F 2 , Cl 2 , Br 2 , ClF, ICl (Sc), IBr (Y), and SF 6 and La with F 2 , SF 6 , Cl 2 , and ClF have been studied at low pressures (6 × 10 −6 to 4 × 10 −4 Torr) using a beam-gas arrangement and extended to the 10 −3 Torr multiple collision pressure range. Contrary to previous reports, the observed chemiluminescent spectra are primarily attributed to emission from the metal monohalides. Extensive pressure and temperature dependence studies and high-level correlated molecular orbital theory calculations of the bond dissociation energies support this conclusion and the attribution of the chemiluminescence. Evidence for the "selective" production of a monohalide excited electronic state is obtained for several of the Sc and Y reactions. All reactions producing the metal monofluorides are first order with respect to the oxidant, while reactions producing the monochlorides and monobromides are found to be "faster than first order" with respect to the oxidant. This difference is associated with the metal halide bond dissociation energies and the metal halide product internal density of states. Analysis of the temperature dependence for six representative reactions indicates that the "selective" excited-state formation of the metal monohalides proceeds via a direct mechanism with negligible activation energy. We compare and contrast the present results with previous experiments and interpretations which have assigned the selective emission from these systems to the group 3 dihalides produced in a two-step reaction sequence analogous to an electron jump process. The current results suggest a distinctly different interpretation of the observed processes in these systems. The observed selectivity observed in these studies is remarkable given the significant number of known and potential excited states in the scandium and yttrium halides as well as their different electronic configurations.

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Section: Resultsmentioning

confidence: 99%

Observation of Selectively Populated Monohalide Excited States from the Reactions of Group 3 Metal (Sc, Y, and La) Monomers and Dimers with Halogen-Containing Molecules

et al. 2022

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Spectroscopy of diatomic ZrF and ZrCl: 760 – 555 nm

Martinez

Morse

2011

The Journal of Chemical Physics

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The optical spectrum of diatomic ZrF has been investigated, with transitions recorded in the range from 14,700 to 18,000 cm(-1). Many bands have been observed, several of which can be grouped into three band systems. Rotationally resolved investigations are hampered by perturbations that are rampant among the excited states, but three unperturbed bands have revealed that the ground state of ZrF has Ω" = 3/2, with a bond length of r(e)'' = 1.854(1) Å. Hot bands originating from v" = 1 provide the ground state vibrational interval, ΔG(1/2)'' = 691.45(2) cm(-1) for (90)Zr(19)F. Based on comparisons to ZrCl and ligand-field considerations, the ZrF ground state is assigned as a (2)Δ(3/2) level deriving from the 3σ(2) 1δ(1) configuration, in agreement with a previous study. In addition to the measurements on ZrF, vibronically resolved spectra of ZrCl have been recorded over the 13,000 to 18,000 cm(-1) range, and four band systems have been identified.

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Density functional theory study of yttrium monohalides

Tong

Cheung

2012

Molecular Physics

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Spin-forbidden cΣ1+3←XΣ+1 band system of YF

Cited by 4 publications

References 23 publications

Observation of Selectively Populated Monohalide Excited States from the Reactions of Group 3 Metal (Sc, Y, and La) Monomers and Dimers with Halogen-Containing Molecules

Observation of Selectively Populated Monohalide Excited States from the Reactions of Group 3 Metal (Sc, Y, and La) Monomers and Dimers with Halogen-Containing Molecules

Spectroscopy of diatomic ZrF and ZrCl: 760 – 555 nm

Density functional theory study of yttrium monohalides

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