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Title: A benchmark photoelectron spectroscopic and theoretical study of the electronic stability of [B 12H 12] 2-

Abstract

We report a joint benchmark study on the electronic stability of closo-dodecaborate [B 12H 12] 2-employing negative ion photoelectron spectroscopy and high level electronic structure methods. The photoelectron spectra of [B 12H 12] 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 coupled cluster with single, double and a perturbative estimate of triple excitations/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 modeled 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 amore » 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.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Purdue Univ., West Lafayette, IN (United States); Univ. Leipzig, Leipzig (Germany)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Univ. of Washington, Seattle, WA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1528908
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 150; Journal Issue: 16; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Aprà, 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.
Aprà, 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.
Aprà, Edoardo, Warneke, Jonas, Xantheas, Sotiris S., and Wang, Xue -Bin. Wed . "A benchmark photoelectron spectroscopic and theoretical study of the electronic stability of [B12H12]2-". United States. doi:10.1063/1.5089510.
@article{osti_1528908,
title = {A benchmark photoelectron spectroscopic and theoretical study of the electronic stability of [B12H12]2-},
author = {Aprà, 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 coupled cluster with single, double and a perturbative estimate of triple excitations/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 modeled 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 = 150,
place = {United States},
year = {2019},
month = {4}
}

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Works referenced in this record:

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