Spectroscopic Characterization, Computational Investigation, and Comparisons of ECX- (E = As, P, and N; X = S and O) Anions

Gao Lei Hou, Bo Chen, Wesley J. Transue, Zheng Yang, Hansjörg Grützmacher, Matthias Driess, Christopher C. Cummins, Weston Thatcher Borden, Xue Bin Wang

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

Three newly synthesized [Na+(221-Kryptofix)] salts containing AsCO-, PCO-, and PCS- anions were successfully electrosprayed into a vacuum, and these three ECX- anions were investigated by negative ion photoelectron spectroscopy (NIPES) along with high-resolution photoelectron imaging spectroscopy. For each ECX- anion, a well-resolved NIPE spectrum was obtained, in which every major peak is split into a doublet. The splittings are attributed to spin-orbit coupling (SOC) in the ECX radicals. Vibrational progressions in the NIPE spectra of ECX- were assigned to the symmetric and the antisymmetric stretching modes in ECX radicals. The electron affinities (EAs) and SO splittings of ECX are determined from the NIPE spectra to be AsCO: EA = 2.414 ± 0.002 eV, SO splitting = 988 cm-1 PCO: EA = 2.670 ± 0.005 eV, SO splitting = 175 cm-1 PCS: EA = 2.850 ± 0.005 eV, SO splitting = 300 cm-1. Calculations using the B3LYP, CASPT2, and CCSD(T) methods all predict linear geometries for both the anions and the neutral radicals. The calculated EAs and SO splittings for ECX are in excellent agreement with the experimentally measured values. The simulated NIPE spectra, which are based on the calculated Franck-Condon factors, and the SO splittings nicely reproduce all of the observed spectral peaks, thus allowing unambiguous spectral assignments. The finding that PCS has the greatest EA of the three triatomic molecules considered here is counterintuitive based upon simple electronegativity considerations, but this finding is understandable in terms of the movement of electron density from phosphorus in the HOMO of PCO- to sulfur in the HOMO of PCS-. Comparisons of the EAs of PCO and PCS with the previously measured EA values for NCO and NCS are made and discussed.

Original languageEnglish (US)
Pages (from-to)8922-8930
Number of pages9
JournalJournal of the American Chemical Society
Volume139
Issue number26
DOIs
StatePublished - Jul 5 2017

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Electron affinity
Anions
Negative ions
Electrons
Photoelectron Spectroscopy
Electronegativity
Photoelectron spectroscopy
Photoelectrons
Sulfur
Orbit
Phosphorus
Vacuum
Stretching
Carrier concentration
Orbits
Salts
Spectroscopy
Imaging techniques
Ions
Molecules

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Hou, Gao Lei ; Chen, Bo ; Transue, Wesley J. ; Yang, Zheng ; Grützmacher, Hansjörg ; Driess, Matthias ; Cummins, Christopher C. ; Borden, Weston Thatcher ; Wang, Xue Bin. / Spectroscopic Characterization, Computational Investigation, and Comparisons of ECX- (E = As, P, and N; X = S and O) Anions. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 26. pp. 8922-8930.
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abstract = "Three newly synthesized [Na+(221-Kryptofix)] salts containing AsCO-, PCO-, and PCS- anions were successfully electrosprayed into a vacuum, and these three ECX- anions were investigated by negative ion photoelectron spectroscopy (NIPES) along with high-resolution photoelectron imaging spectroscopy. For each ECX- anion, a well-resolved NIPE spectrum was obtained, in which every major peak is split into a doublet. The splittings are attributed to spin-orbit coupling (SOC) in the ECX• radicals. Vibrational progressions in the NIPE spectra of ECX- were assigned to the symmetric and the antisymmetric stretching modes in ECX• radicals. The electron affinities (EAs) and SO splittings of ECX• are determined from the NIPE spectra to be AsCO•: EA = 2.414 ± 0.002 eV, SO splitting = 988 cm-1 PCO•: EA = 2.670 ± 0.005 eV, SO splitting = 175 cm-1 PCS•: EA = 2.850 ± 0.005 eV, SO splitting = 300 cm-1. Calculations using the B3LYP, CASPT2, and CCSD(T) methods all predict linear geometries for both the anions and the neutral radicals. The calculated EAs and SO splittings for ECX• are in excellent agreement with the experimentally measured values. The simulated NIPE spectra, which are based on the calculated Franck-Condon factors, and the SO splittings nicely reproduce all of the observed spectral peaks, thus allowing unambiguous spectral assignments. The finding that PCS• has the greatest EA of the three triatomic molecules considered here is counterintuitive based upon simple electronegativity considerations, but this finding is understandable in terms of the movement of electron density from phosphorus in the HOMO of PCO- to sulfur in the HOMO of PCS-. Comparisons of the EAs of PCO• and PCS• with the previously measured EA values for NCO• and NCS• are made and discussed.",
author = "Hou, {Gao Lei} and Bo Chen and Transue, {Wesley J.} and Zheng Yang and Hansj{\"o}rg Gr{\"u}tzmacher and Matthias Driess and Cummins, {Christopher C.} and Borden, {Weston Thatcher} and Wang, {Xue Bin}",
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Hou, GL, Chen, B, Transue, WJ, Yang, Z, Grützmacher, H, Driess, M, Cummins, CC, Borden, WT & Wang, XB 2017, 'Spectroscopic Characterization, Computational Investigation, and Comparisons of ECX- (E = As, P, and N; X = S and O) Anions', Journal of the American Chemical Society, vol. 139, no. 26, pp. 8922-8930. https://doi.org/10.1021/jacs.7b02984

Spectroscopic Characterization, Computational Investigation, and Comparisons of ECX- (E = As, P, and N; X = S and O) Anions. / Hou, Gao Lei; Chen, Bo; Transue, Wesley J.; Yang, Zheng; Grützmacher, Hansjörg; Driess, Matthias; Cummins, Christopher C.; Borden, Weston Thatcher; Wang, Xue Bin.

In: Journal of the American Chemical Society, Vol. 139, No. 26, 05.07.2017, p. 8922-8930.

Research output: Contribution to journalArticle

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T1 - Spectroscopic Characterization, Computational Investigation, and Comparisons of ECX- (E = As, P, and N; X = S and O) Anions

AU - Hou, Gao Lei

AU - Chen, Bo

AU - Transue, Wesley J.

AU - Yang, Zheng

AU - Grützmacher, Hansjörg

AU - Driess, Matthias

AU - Cummins, Christopher C.

AU - Borden, Weston Thatcher

AU - Wang, Xue Bin

PY - 2017/7/5

Y1 - 2017/7/5

N2 - Three newly synthesized [Na+(221-Kryptofix)] salts containing AsCO-, PCO-, and PCS- anions were successfully electrosprayed into a vacuum, and these three ECX- anions were investigated by negative ion photoelectron spectroscopy (NIPES) along with high-resolution photoelectron imaging spectroscopy. For each ECX- anion, a well-resolved NIPE spectrum was obtained, in which every major peak is split into a doublet. The splittings are attributed to spin-orbit coupling (SOC) in the ECX• radicals. Vibrational progressions in the NIPE spectra of ECX- were assigned to the symmetric and the antisymmetric stretching modes in ECX• radicals. The electron affinities (EAs) and SO splittings of ECX• are determined from the NIPE spectra to be AsCO•: EA = 2.414 ± 0.002 eV, SO splitting = 988 cm-1 PCO•: EA = 2.670 ± 0.005 eV, SO splitting = 175 cm-1 PCS•: EA = 2.850 ± 0.005 eV, SO splitting = 300 cm-1. Calculations using the B3LYP, CASPT2, and CCSD(T) methods all predict linear geometries for both the anions and the neutral radicals. The calculated EAs and SO splittings for ECX• are in excellent agreement with the experimentally measured values. The simulated NIPE spectra, which are based on the calculated Franck-Condon factors, and the SO splittings nicely reproduce all of the observed spectral peaks, thus allowing unambiguous spectral assignments. The finding that PCS• has the greatest EA of the three triatomic molecules considered here is counterintuitive based upon simple electronegativity considerations, but this finding is understandable in terms of the movement of electron density from phosphorus in the HOMO of PCO- to sulfur in the HOMO of PCS-. Comparisons of the EAs of PCO• and PCS• with the previously measured EA values for NCO• and NCS• are made and discussed.

AB - Three newly synthesized [Na+(221-Kryptofix)] salts containing AsCO-, PCO-, and PCS- anions were successfully electrosprayed into a vacuum, and these three ECX- anions were investigated by negative ion photoelectron spectroscopy (NIPES) along with high-resolution photoelectron imaging spectroscopy. For each ECX- anion, a well-resolved NIPE spectrum was obtained, in which every major peak is split into a doublet. The splittings are attributed to spin-orbit coupling (SOC) in the ECX• radicals. Vibrational progressions in the NIPE spectra of ECX- were assigned to the symmetric and the antisymmetric stretching modes in ECX• radicals. The electron affinities (EAs) and SO splittings of ECX• are determined from the NIPE spectra to be AsCO•: EA = 2.414 ± 0.002 eV, SO splitting = 988 cm-1 PCO•: EA = 2.670 ± 0.005 eV, SO splitting = 175 cm-1 PCS•: EA = 2.850 ± 0.005 eV, SO splitting = 300 cm-1. Calculations using the B3LYP, CASPT2, and CCSD(T) methods all predict linear geometries for both the anions and the neutral radicals. The calculated EAs and SO splittings for ECX• are in excellent agreement with the experimentally measured values. The simulated NIPE spectra, which are based on the calculated Franck-Condon factors, and the SO splittings nicely reproduce all of the observed spectral peaks, thus allowing unambiguous spectral assignments. The finding that PCS• has the greatest EA of the three triatomic molecules considered here is counterintuitive based upon simple electronegativity considerations, but this finding is understandable in terms of the movement of electron density from phosphorus in the HOMO of PCO- to sulfur in the HOMO of PCS-. Comparisons of the EAs of PCO• and PCS• with the previously measured EA values for NCO• and NCS• are made and discussed.

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