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Title: Electronic structures and binding motifs of sodium polysulfide clusters NaSn- (n = 5-9): a joint negative ion photoelectron spectroscopy and computational investigation

Abstract

Motivated by the significant biological functions of polysulfides in life processes and important applications of sodium polysulfides in battery sciences, herein we report a joint experimental and computational study on the electronic and geometric structures of a series of NaSn- (n = 5-9) clusters. The cryogenic, size-selective, negative ion photoelectron spectroscopy (NIPES) is employed to obtain their photoelectron spectra, in which distinctive spectral features with electron binding energy (EBE) up to 6.4 eV are unraveled. The EBE of the first peak in each spectrum for NaSn- (n =5-9), assigned to the transition from the ground state of anion to the ground state of each neutral radical, is observed to increase with cluster size. The vertical detachment energies (VDEs), determined from the first peak maximum, are 3.43 ± 0.02, 3.57 ± 0.02, 3.82 ± 0.03, 3.86 ± 0.02, and 4.00 ± 0.02 eV and the adiabatic detachment energies (ADEs), determined by the onset of the first peak, are 3.27 ± 0.05, 3.44 ± 0.05, 3.65 ± 0.05, 3.75 ± 0.05, and 3.93 ± 0.05 eV, for n = 5-9, respectively. A plural of low-lying isomers of anions are screened and identified with density functional theory calculations, showing that all featuring preferencemore » for a chain-like polysulfide moiety electrostatically interacted with a sodium cation. The calculated VDEs and ADEs using the high-level CCSD(T)/aug-cc-pVTZ method are in excellent agreement with experimental results, further confirming the identified isomers as most stable ones. Further analyses based on the excited-state transition, molecular orbitals and natural population charge are performed to assign all observed spectral bands along the binding energy axis, suggesting that the electron detachment process and observed excitations mainly derived from the polysulfide chain of NaSn- clusters. This work provides a fundamental understanding of the intrinsic molecular properties of sodium polysulfide systems, which widely exist in life science and sodium-sulfur cells.« less

Authors:
 [1];  [2];  [2];  [1];  [2]; ORCiD logo [3];  [2]
  1. UNIVERSITY PROGRAMS
  2. East China Normal University
  3. BATTELLE (PACIFIC NW LAB)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1545053
Report Number(s):
PNNL-SA-142853
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 150; Journal Issue: 24
Country of Publication:
United States
Language:
English

Citation Formats

Li, Zhipeng, Hu, Zhubin, Jiang, Yanrong, Yuan, Qinqin, Sun, Haitao, Wang, Xue-Bin, and Sun, Zhenrong. Electronic structures and binding motifs of sodium polysulfide clusters NaSn- (n = 5-9): a joint negative ion photoelectron spectroscopy and computational investigation. United States: N. p., 2019. Web. doi:10.1063/1.5100733.
Li, Zhipeng, Hu, Zhubin, Jiang, Yanrong, Yuan, Qinqin, Sun, Haitao, Wang, Xue-Bin, & Sun, Zhenrong. Electronic structures and binding motifs of sodium polysulfide clusters NaSn- (n = 5-9): a joint negative ion photoelectron spectroscopy and computational investigation. United States. doi:10.1063/1.5100733.
Li, Zhipeng, Hu, Zhubin, Jiang, Yanrong, Yuan, Qinqin, Sun, Haitao, Wang, Xue-Bin, and Sun, Zhenrong. Fri . "Electronic structures and binding motifs of sodium polysulfide clusters NaSn- (n = 5-9): a joint negative ion photoelectron spectroscopy and computational investigation". United States. doi:10.1063/1.5100733.
@article{osti_1545053,
title = {Electronic structures and binding motifs of sodium polysulfide clusters NaSn- (n = 5-9): a joint negative ion photoelectron spectroscopy and computational investigation},
author = {Li, Zhipeng and Hu, Zhubin and Jiang, Yanrong and Yuan, Qinqin and Sun, Haitao and Wang, Xue-Bin and Sun, Zhenrong},
abstractNote = {Motivated by the significant biological functions of polysulfides in life processes and important applications of sodium polysulfides in battery sciences, herein we report a joint experimental and computational study on the electronic and geometric structures of a series of NaSn- (n = 5-9) clusters. The cryogenic, size-selective, negative ion photoelectron spectroscopy (NIPES) is employed to obtain their photoelectron spectra, in which distinctive spectral features with electron binding energy (EBE) up to 6.4 eV are unraveled. The EBE of the first peak in each spectrum for NaSn- (n =5-9), assigned to the transition from the ground state of anion to the ground state of each neutral radical, is observed to increase with cluster size. The vertical detachment energies (VDEs), determined from the first peak maximum, are 3.43 ± 0.02, 3.57 ± 0.02, 3.82 ± 0.03, 3.86 ± 0.02, and 4.00 ± 0.02 eV and the adiabatic detachment energies (ADEs), determined by the onset of the first peak, are 3.27 ± 0.05, 3.44 ± 0.05, 3.65 ± 0.05, 3.75 ± 0.05, and 3.93 ± 0.05 eV, for n = 5-9, respectively. A plural of low-lying isomers of anions are screened and identified with density functional theory calculations, showing that all featuring preference for a chain-like polysulfide moiety electrostatically interacted with a sodium cation. The calculated VDEs and ADEs using the high-level CCSD(T)/aug-cc-pVTZ method are in excellent agreement with experimental results, further confirming the identified isomers as most stable ones. Further analyses based on the excited-state transition, molecular orbitals and natural population charge are performed to assign all observed spectral bands along the binding energy axis, suggesting that the electron detachment process and observed excitations mainly derived from the polysulfide chain of NaSn- clusters. This work provides a fundamental understanding of the intrinsic molecular properties of sodium polysulfide systems, which widely exist in life science and sodium-sulfur cells.},
doi = {10.1063/1.5100733},
journal = {Journal of Chemical Physics},
number = 24,
volume = 150,
place = {United States},
year = {2019},
month = {6}
}

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