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

doi:10.1002/anie.201906904

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)

Journal Article · Wed Sep 04 00:00:00 EDT 2019 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201906904· OSTI ID:1560280

Yuan, Qinqin ^[1]; Tambornino, Frank ^[2]; Hinz, Alexander ^[3]; Borden, Weston Thatcher ^[4]; Goicoechea, Jose M. ^[5]; Chen, Bo ^[6]; ^[1]

Physical Sciences Division Pacific Northwest National Laboratory 902 Battelle Boulevard, P. O. Box 999, MS K8-88 Richland WA 99352 USA
Department of Chemistry University of Oxford Chemistry Research Laboratory 12 Mansfield Road Oxford OX1 3TA UK, Fachbereich Chemie Philipps-Universität Marburg Hans-Meerwein-Strasse 4 35043 Marburg Germany
Karlsruhe Institut of Technology (KIT) Institute for Inorganic Chemistry (AOC) Engesserstraße 15, Geb. 30.45 76131 Karlsruhe Germany
Department of Chemistry and the Center for Advanced Scientific Computing and Modeling University of North Texas 1155 Union Circle, #305070 Denton TX 76203-5070 USA
Department of Chemistry University of Oxford Chemistry Research Laboratory 12 Mansfield Road Oxford OX1 3TA UK
Department of Chemistry Pennsylvania State University University Park PA 16801 USA

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.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

OSTI ID:: 1560280

Alternate ID(s):: OSTI ID: 1577106

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 42 Vol. 58; ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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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)