Photoelectron Spectroscopy and Theoretical Studies of PCSe, AsCS, AsCSe, and NCSe: Insights into the Electronic Structures of the Whole Family of ECX Anions (E=N, P, As; X=O, S, Se)

Qinqin Yuan, Frank Tambornino, Alexander Hinz, Weston Thatcher Borden, Jose M. Goicoechea, Bo Chen, Xue Bin Wang

Research output: Contribution to journalArticle

Abstract

The newly synthesized phosphorus- and arsenic-containing analogues of the thio- and seleno-cyanate anions, PCSe, AsCS, and AsCSe, as well as the known ion NCSe were investigated in the gas phase by negative-ion photoelectron spectroscopy (NIPES), velocity-map imaging (VMI) spectroscopy, and quantum-chemical computations. The electron affinities (EA), spin–orbit (SO) splittings, and “symmetric”/“asymmetric” stretching frequencies of the neutral radicals ECX. (E=N, P, As; X=S, Se), generated by electron detachment from the corresponding anions, were obtained from the spectra. The calculated EAs, SO splittings, and vibrational frequencies are in excellent agreement with the experimental measurements. These newly obtained values, when combined with those previously determined for the lighter analogues, show interesting trends on descending the pnictogen and chalcogen series. These trends are rationalized based on electronegativity arguments, the electron distributions in the HOMOs, and NBO/NRT analyses.

Original languageEnglish (US)
Pages (from-to)15062-15068
Number of pages7
JournalAngewandte Chemie - International Edition
Volume58
Issue number42
DOIs
StatePublished - Oct 14 2019

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Photoelectron spectroscopy
Electronic structure
Anions
Chalcogens
Negative ions
Cyanates
Electron affinity
Electronegativity
Electrons
Arsenic
Vibrational spectra
Phosphorus
Stretching
Gases
Spectroscopy
Ions
Imaging techniques

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

Cite this

Yuan, Qinqin ; Tambornino, Frank ; Hinz, Alexander ; Borden, Weston Thatcher ; Goicoechea, Jose M. ; Chen, Bo ; Wang, Xue Bin. / Photoelectron Spectroscopy and Theoretical Studies of PCSe, AsCS, AsCSe, and NCSe : Insights into the Electronic Structures of the Whole Family of ECX Anions (E=N, P, As; X=O, S, Se). In: Angewandte Chemie - International Edition. 2019 ; Vol. 58, No. 42. pp. 15062-15068.
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abstract = "The newly synthesized phosphorus- and arsenic-containing analogues of the thio- and seleno-cyanate anions, PCSe−, AsCS−, and AsCSe−, as well as the known ion NCSe− were investigated in the gas phase by negative-ion photoelectron spectroscopy (NIPES), velocity-map imaging (VMI) spectroscopy, and quantum-chemical computations. The electron affinities (EA), spin–orbit (SO) splittings, and “symmetric”/“asymmetric” stretching frequencies of the neutral radicals ECX. (E=N, P, As; X=S, Se), generated by electron detachment from the corresponding anions, were obtained from the spectra. The calculated EAs, SO splittings, and vibrational frequencies are in excellent agreement with the experimental measurements. These newly obtained values, when combined with those previously determined for the lighter analogues, show interesting trends on descending the pnictogen and chalcogen series. These trends are rationalized based on electronegativity arguments, the electron distributions in the HOMOs, and NBO/NRT analyses.",
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Photoelectron Spectroscopy and Theoretical Studies of PCSe, AsCS, AsCSe, and NCSe : Insights into the Electronic Structures of the Whole Family of ECX Anions (E=N, P, As; X=O, S, Se). / Yuan, Qinqin; Tambornino, Frank; Hinz, Alexander; Borden, Weston Thatcher; Goicoechea, Jose M.; Chen, Bo; Wang, Xue Bin.

In: Angewandte Chemie - International Edition, Vol. 58, No. 42, 14.10.2019, p. 15062-15068.

Research output: Contribution to journalArticle

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AU - Chen, Bo

AU - Wang, Xue Bin

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