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)
- UNIVERSITY PROGRAMS
- Oxford University
- Karlsruhe Institute of Technology
- University of North Texas
- Pennsylvania State University
- BATTELLE (PACIFIC NW LAB)
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.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 1577106
- Report Number(s):
- PNNL-SA-144030
- Journal Information:
- Angewandte Chemie International Edition, Vol. 58, Issue 42
- Country of Publication:
- United States
- Language:
- English
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