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Title: Magnetic-bottle and velocity-map imaging photoelectron spectroscopy of APS- (A = C14H10 or anthracene): electron structure, spin-orbit coupling of APS•, and dipole-bound state of APS-

Abstract

Gaseous dibenzo-7-phosphanorbornadiene P-sulfide anions APS- (A = C14H10 or anthracene) were generated via electrospray ionization, and characterized by magnetic-bottle photoelectron spectroscopy, velocity-map imaging (VMI) photoelectron spectroscopy, and quantum chemical calculations. The electron affinity (EA) and spin-orbit splitting (SO) of the APS• radical are determined from the photoelectron spectra and Franck-Condon factor simulations to be EA = 2.62 ± 0.05 eV and SO splitting = 43 ± 7 meV. VMI photoelectron images show strong and sharp peaks near detachment threshold with an identical electron kinetic energy (eKE) of 17.9 meV at three different detachment wavelengths, which are therefore assigned due to autodetachment from dipole-bound anion states. The B3LYP/6-31++g(d,p) calculations indicate APS• has a dipole moment of 3.31 Debye, large enough to support a dipole-bound electron.

Authors:
 [1];  [2];  [1];  [3];  [1];  [1]; ORCiD logo [2];  [3]; ORCiD logo [2]
  1. UNIVERSITY PROGRAMS
  2. BATTELLE (PACIFIC NW LAB)
  3. Massachusetts Institute of Technology
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1578147
Report Number(s):
PNNL-SA-135150
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Chinese Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 31; Journal Issue: 4
Country of Publication:
United States
Language:
English
Subject:
Dibenzo-7-phosphanorbornadiene P-sulfide, electron structure, spin-orbit coupling, dipole-bound state, VMI photoelectron spectroscopy

Citation Formats

Yuan, Qinqin, Yang, Zheng, Li, Renzhong, Transue, Wesley J., Li, Zhipeng, Jiang, Ling, Govind, Niranjan, Cummins, Christopher C., and Wang, Xue-Bin. Magnetic-bottle and velocity-map imaging photoelectron spectroscopy of APS- (A = C14H10 or anthracene): electron structure, spin-orbit coupling of APS•, and dipole-bound state of APS-. United States: N. p., 2018. Web. doi:10.1063/1674-0068/31/cjcp1805114.
Yuan, Qinqin, Yang, Zheng, Li, Renzhong, Transue, Wesley J., Li, Zhipeng, Jiang, Ling, Govind, Niranjan, Cummins, Christopher C., & Wang, Xue-Bin. Magnetic-bottle and velocity-map imaging photoelectron spectroscopy of APS- (A = C14H10 or anthracene): electron structure, spin-orbit coupling of APS•, and dipole-bound state of APS-. United States. doi:10.1063/1674-0068/31/cjcp1805114.
Yuan, Qinqin, Yang, Zheng, Li, Renzhong, Transue, Wesley J., Li, Zhipeng, Jiang, Ling, Govind, Niranjan, Cummins, Christopher C., and Wang, Xue-Bin. Sat . "Magnetic-bottle and velocity-map imaging photoelectron spectroscopy of APS- (A = C14H10 or anthracene): electron structure, spin-orbit coupling of APS•, and dipole-bound state of APS-". United States. doi:10.1063/1674-0068/31/cjcp1805114.
@article{osti_1578147,
title = {Magnetic-bottle and velocity-map imaging photoelectron spectroscopy of APS- (A = C14H10 or anthracene): electron structure, spin-orbit coupling of APS•, and dipole-bound state of APS-},
author = {Yuan, Qinqin and Yang, Zheng and Li, Renzhong and Transue, Wesley J. and Li, Zhipeng and Jiang, Ling and Govind, Niranjan and Cummins, Christopher C. and Wang, Xue-Bin},
abstractNote = {Gaseous dibenzo-7-phosphanorbornadiene P-sulfide anions APS- (A = C14H10 or anthracene) were generated via electrospray ionization, and characterized by magnetic-bottle photoelectron spectroscopy, velocity-map imaging (VMI) photoelectron spectroscopy, and quantum chemical calculations. The electron affinity (EA) and spin-orbit splitting (SO) of the APS• radical are determined from the photoelectron spectra and Franck-Condon factor simulations to be EA = 2.62 ± 0.05 eV and SO splitting = 43 ± 7 meV. VMI photoelectron images show strong and sharp peaks near detachment threshold with an identical electron kinetic energy (eKE) of 17.9 meV at three different detachment wavelengths, which are therefore assigned due to autodetachment from dipole-bound anion states. The B3LYP/6-31++g(d,p) calculations indicate APS• has a dipole moment of 3.31 Debye, large enough to support a dipole-bound electron.},
doi = {10.1063/1674-0068/31/cjcp1805114},
journal = {Chinese Journal of Chemical Physics},
number = 4,
volume = 31,
place = {United States},
year = {2018},
month = {8}
}

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