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 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 thatmore » 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:

Aprà, Edoardo  ^[1];

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• Search DOE PAGES for ORCID "0000-0001-5955-0734"

Warneke, Jonas  ^[2];

• Search DOE PAGES for author "Warneke, Jonas"
• Search DOE PAGES for ORCID "0000-0002-3233-7412"

Xantheas, Sotiris S.  ^[3];

• Search DOE PAGES for author "Xantheas, Sotiris S."
• Search DOE PAGES for ORCID "0000-0002-6303-1037"

Wang, Xue -Bin  ^[1]

• Search DOE PAGES for author "Wang, Xue -Bin"
• Search DOE PAGES for ORCID "0000-0001-8326-1780"

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+ Show Author Affiliations

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:

Wed Apr 24 00:00:00 EDT 2019

Research Org.:

Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and 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