Halide-Nitrogen Gas-Phase Clusters: Anion Photoelectron Spectroscopy and High Level ab Initio Calculations

K.M.L. Lapere, Marcus Kettner, P.D. Watson, Allan Mckinley, Duncan Wild

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

© 2015 American Chemical Society. The gas phase anion photoelectron spectra are presented for the halide-nitrogen clusters X-⋯(N2)n, where X = Br and I and n ≤ 5. Electron binding energies for each cluster in the halide series are determined, with no evidence observed for first solvation shell closure in either series. High level ab initio calculations at the CCSD(T) level of theory are presented for the anion and neutral halogen-nitrogen complexes. For the anion species, two minima are predicted corresponding to a loosely bound C2v "T-shaped" species and to a higher energy covalently bound "triangle" C2v symmetry geometry. For the neutral species, three stationary points were located, two of which display similar form to the anion minima and a third which is linear, i.e., C∞v symmetry. The "T-shaped" geometry is a transition state linking equivalent C∞v symmetry minima. Cluster dissociation energies (D0) were determined, for both anion and neutral global minima at the CCSD(T) complete basis set limit, to be 7.8 kJ mol-1 and 7.0 kJ mol-1 and 3.5 kJ mol-1 and 5.0 kJ mol-1 for the bromine and iodine species, respectively.
Original languageEnglish
Pages (from-to)9722-9728
JournalJournal of Physical Chemistry A
Volume119
Issue number37
Early online date24 Aug 2015
DOIs
Publication statusPublished - Sep 2015

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Photoelectron spectroscopy
halides
Anions
Nitrogen
Gases
photoelectron spectroscopy
vapor phases
anions
nitrogen
symmetry
Bromine
Halogens
Geometry
Solvation
bromine
Photoelectrons
geometry
Binding energy
triangles
Iodine

Cite this

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title = "Halide-Nitrogen Gas-Phase Clusters: Anion Photoelectron Spectroscopy and High Level ab Initio Calculations",
abstract = "{\circledC} 2015 American Chemical Society. The gas phase anion photoelectron spectra are presented for the halide-nitrogen clusters X-⋯(N2)n, where X = Br and I and n ≤ 5. Electron binding energies for each cluster in the halide series are determined, with no evidence observed for first solvation shell closure in either series. High level ab initio calculations at the CCSD(T) level of theory are presented for the anion and neutral halogen-nitrogen complexes. For the anion species, two minima are predicted corresponding to a loosely bound C2v {"}T-shaped{"} species and to a higher energy covalently bound {"}triangle{"} C2v symmetry geometry. For the neutral species, three stationary points were located, two of which display similar form to the anion minima and a third which is linear, i.e., C∞v symmetry. The {"}T-shaped{"} geometry is a transition state linking equivalent C∞v symmetry minima. Cluster dissociation energies (D0) were determined, for both anion and neutral global minima at the CCSD(T) complete basis set limit, to be 7.8 kJ mol-1 and 7.0 kJ mol-1 and 3.5 kJ mol-1 and 5.0 kJ mol-1 for the bromine and iodine species, respectively.",
author = "K.M.L. Lapere and Marcus Kettner and P.D. Watson and Allan Mckinley and Duncan Wild",
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Halide-Nitrogen Gas-Phase Clusters: Anion Photoelectron Spectroscopy and High Level ab Initio Calculations. / Lapere, K.M.L.; Kettner, Marcus; Watson, P.D.; Mckinley, Allan; Wild, Duncan.

In: Journal of Physical Chemistry A, Vol. 119, No. 37, 09.2015, p. 9722-9728.

Research output: Contribution to journalArticle

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T1 - Halide-Nitrogen Gas-Phase Clusters: Anion Photoelectron Spectroscopy and High Level ab Initio Calculations

AU - Lapere, K.M.L.

AU - Kettner, Marcus

AU - Watson, P.D.

AU - Mckinley, Allan

AU - Wild, Duncan

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N2 - © 2015 American Chemical Society. The gas phase anion photoelectron spectra are presented for the halide-nitrogen clusters X-⋯(N2)n, where X = Br and I and n ≤ 5. Electron binding energies for each cluster in the halide series are determined, with no evidence observed for first solvation shell closure in either series. High level ab initio calculations at the CCSD(T) level of theory are presented for the anion and neutral halogen-nitrogen complexes. For the anion species, two minima are predicted corresponding to a loosely bound C2v "T-shaped" species and to a higher energy covalently bound "triangle" C2v symmetry geometry. For the neutral species, three stationary points were located, two of which display similar form to the anion minima and a third which is linear, i.e., C∞v symmetry. The "T-shaped" geometry is a transition state linking equivalent C∞v symmetry minima. Cluster dissociation energies (D0) were determined, for both anion and neutral global minima at the CCSD(T) complete basis set limit, to be 7.8 kJ mol-1 and 7.0 kJ mol-1 and 3.5 kJ mol-1 and 5.0 kJ mol-1 for the bromine and iodine species, respectively.

AB - © 2015 American Chemical Society. The gas phase anion photoelectron spectra are presented for the halide-nitrogen clusters X-⋯(N2)n, where X = Br and I and n ≤ 5. Electron binding energies for each cluster in the halide series are determined, with no evidence observed for first solvation shell closure in either series. High level ab initio calculations at the CCSD(T) level of theory are presented for the anion and neutral halogen-nitrogen complexes. For the anion species, two minima are predicted corresponding to a loosely bound C2v "T-shaped" species and to a higher energy covalently bound "triangle" C2v symmetry geometry. For the neutral species, three stationary points were located, two of which display similar form to the anion minima and a third which is linear, i.e., C∞v symmetry. The "T-shaped" geometry is a transition state linking equivalent C∞v symmetry minima. Cluster dissociation energies (D0) were determined, for both anion and neutral global minima at the CCSD(T) complete basis set limit, to be 7.8 kJ mol-1 and 7.0 kJ mol-1 and 3.5 kJ mol-1 and 5.0 kJ mol-1 for the bromine and iodine species, respectively.

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