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Title: A benchmark photoelectron spectroscopic and theoretical study of the electronic stability of [B12H12]2-

Abstract

We report a joint benchmark study on the electronic stability of closo-dodecaborate [B12H12]2- employing negative ion photoelectron spectroscopy and high level electronic structure methods. The photoelectron spectra of [B12H12]2-, measured at 266, 193 and 157 nm, yield the Adiabatic and Vertical Detachment Energies (ADE and VDE) of this dianion at 0.93 ± 0.05 eV and 1.15 ± 0.05 eV, respectively, along with a ~ 3 eV Repulsive Coulomb Barrier (RCB) against electron detachment. Theoretical calculations at various levels of electronic structure theory confirm the high stability of this dianion. The ADE and VDE values calculated at the CCSD(T)/aug-cc-PVQZ level are 0.92, and 1.16 eV, in excellent agreement with the experimental benchmark values. The comparison between the experimental and the theoretical values obtained at different levels of theory indicate that the PBE0 density functional represents a cost-effective method of sufficient accuracy to describe the molecular properties of this dianion and associated compounds. The theoretical RCB was modelled after the electrostatic potential (ESP) and point charge method (PCM) along three different detachment pathways, viz. along the B-H bond, perpendicular to a B-B bond, and normal to a B-B-B triangle. It was found that detachment of the electron along the B-H bond ismore » preferred, as this pathway is associated with RCBs between 2.3 eV (PCM) and 3.3 eV (ESP), values that bracket the experimental estimate of ~ 3 eV.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [1]
  1. BATTELLE (PACIFIC NW LAB)
  2. UNIVERSITY PROGRAMS
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1530826
Report Number(s):
PNNL-SA-140650
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 105; Journal Issue: 16
Country of Publication:
United States
Language:
English

Citation Formats

Apra, Edoardo, Warneke, Jonas, Xantheas, Sotiris S., and Wang, Xue-Bin. A benchmark photoelectron spectroscopic and theoretical study of the electronic stability of [B12H12]2-. United States: N. p., 2019. Web. doi:10.1063/1.5089510.
Apra, Edoardo, Warneke, Jonas, Xantheas, Sotiris S., & Wang, Xue-Bin. A benchmark photoelectron spectroscopic and theoretical study of the electronic stability of [B12H12]2-. United States. doi:10.1063/1.5089510.
Apra, Edoardo, Warneke, Jonas, Xantheas, Sotiris S., and Wang, Xue-Bin. Sun . "A benchmark photoelectron spectroscopic and theoretical study of the electronic stability of [B12H12]2-". United States. doi:10.1063/1.5089510.
@article{osti_1530826,
title = {A benchmark photoelectron spectroscopic and theoretical study of the electronic stability of [B12H12]2-},
author = {Apra, Edoardo and Warneke, Jonas and Xantheas, Sotiris S. and Wang, Xue-Bin},
abstractNote = {We report a joint benchmark study on the electronic stability of closo-dodecaborate [B12H12]2- employing negative ion photoelectron spectroscopy and high level electronic structure methods. The photoelectron spectra of [B12H12]2-, measured at 266, 193 and 157 nm, yield the Adiabatic and Vertical Detachment Energies (ADE and VDE) of this dianion at 0.93 ± 0.05 eV and 1.15 ± 0.05 eV, respectively, along with a ~ 3 eV Repulsive Coulomb Barrier (RCB) against electron detachment. Theoretical calculations at various levels of electronic structure theory confirm the high stability of this dianion. The ADE and VDE values calculated at the CCSD(T)/aug-cc-PVQZ level are 0.92, and 1.16 eV, in excellent agreement with the experimental benchmark values. The comparison between the experimental and the theoretical values obtained at different levels of theory indicate that the PBE0 density functional represents a cost-effective method of sufficient accuracy to describe the molecular properties of this dianion and associated compounds. The theoretical RCB was modelled after the electrostatic potential (ESP) and point charge method (PCM) along three different detachment pathways, viz. along the B-H bond, perpendicular to a B-B bond, and normal to a B-B-B triangle. It was found that detachment of the electron along the B-H bond is preferred, as this pathway is associated with RCBs between 2.3 eV (PCM) and 3.3 eV (ESP), values that bracket the experimental estimate of ~ 3 eV.},
doi = {10.1063/1.5089510},
journal = {Journal of Chemical Physics},
number = 16,
volume = 105,
place = {United States},
year = {2019},
month = {4}
}

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