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Title: 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, and As; X = O, S, and Se)

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” / “antisymmetric” stretching frequencies (?1 and ?2) of the neutral radicals ECX• (E = N, P and As, X = S and 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 measured values. 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 on the basis of electronegativity arguments, the electron distribution in the HOMO, and NBO/NRT analyses.

Authors:
 [1];  [2];  [3];  [4];  [2];  [5];  [6]
  1. UNIVERSITY PROGRAMS
  2. Oxford University
  3. Karlsruhe Institute of Technology
  4. University of North Texas
  5. Pennsylvania State University
  6. BATTELLE (PACIFIC NW LAB)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1577106
Report Number(s):
PNNL-SA-144030
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Angewandte Chemie International Edition
Additional Journal Information:
Journal Volume: 58; Journal Issue: 42
Country of Publication:
United States
Language:
English

Citation Formats

Yuan, Qinqin, Tambornino, Frank, Hinz, Alexander, Borden, Weston, Goicoechea, Jose M., Chen, Bo, and Wang, Xuebin. 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, and As; X = O, S, and Se). United States: N. p., 2019. Web. doi:10.1002/anie.201906904.
Yuan, Qinqin, Tambornino, Frank, Hinz, Alexander, Borden, Weston, Goicoechea, Jose M., Chen, Bo, & Wang, Xuebin. 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, and As; X = O, S, and Se). United States. doi:10.1002/anie.201906904.
Yuan, Qinqin, Tambornino, Frank, Hinz, Alexander, Borden, Weston, Goicoechea, Jose M., Chen, Bo, and Wang, Xuebin. Mon . "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, and As; X = O, S, and Se)". United States. doi:10.1002/anie.201906904.
@article{osti_1577106,
title = {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, and As; X = O, S, and Se)},
author = {Yuan, Qinqin and Tambornino, Frank and Hinz, Alexander and Borden, Weston and Goicoechea, Jose M. and Chen, Bo and Wang, Xuebin},
abstractNote = {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” / “antisymmetric” stretching frequencies (?1 and ?2) of the neutral radicals ECX• (E = N, P and As, X = S and 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 measured values. 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 on the basis of electronegativity arguments, the electron distribution in the HOMO, and NBO/NRT analyses.},
doi = {10.1002/anie.201906904},
journal = {Angewandte Chemie International Edition},
number = 42,
volume = 58,
place = {United States},
year = {2019},
month = {10}
}

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