Electronic and Molecular Structures of the CeB6 Monomer

Mason, Jarrett L.; Harb, Hassan; Huizenga, Caleb D.; Ewigleben, Joshua C.; Topolski, Josey E.; Hratchian, Hrant P.; Jarrold, Caroline Chick

doi:10.1021/acs.jpca.8b12399

Electronic and Molecular Structures of the CeB₆ Monomer

Journal Article · Thu Feb 21 00:00:00 EST 2019 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.8b12399· OSTI ID:1737556

Mason, Jarrett L. ^[1]; Harb, Hassan ^[2]; Huizenga, Caleb D. ^[3]; Ewigleben, Joshua C. ^[3]; Topolski, Josey E. ^[3]; ^[2]; ^[3]

Indiana Univ., Bloomington, IN (United States); Indiana University
Univ. of California, Merced, CA (United States)
Indiana Univ., Bloomington, IN (United States)

The electronic and molecular structure of the CeB₆ molecular unit has been probed by anion PE spectroscopy and DFT calculations to gain insight into structural and electronic relaxation on edge and corner sites of this ionic material. While boron in bulk lanthanide hexaboride materials assumes octahedral B₆^3– units, the monomer assumes a less compact structure to delocalize the charge. Two competitive molecular structures were identified for the anion and neutral species, which include a boat-like structure and a planar or near-planar teardrop structure. Ce adopts different orbital occupancies in the two isomers; the boat-like structure has a 4f superconfiguration while the teardrop favors a 4f 6s occupancy. The B₆ ligand in these structures carries a charge of –4 and –3, respectively. The teardrop structure, which was calculated to be isoenergetic with the boat structure, was most consistent with the experimental spectrum. B₆-local orbitals crowd the energy window between the Ce 4f and 6s (HOMO) orbitals. A low-lying transition from the B-based orbitals is observed slightly less than 1 eV above the ground state. Here, the results suggest that edge and corner conductivity involves stabilized, highly diffuse 6s orbitals or bands rather than the bulk-favored 5d band. High-spin and open-shell low-spin states were calculated to be very close in energy for both the anion and neutral, a characteristic that reflects how decoupled the 4f electron is from the B₆ 2p- and Ce 6s-based molecular orbitals.

View Accepted Manuscript (DOE)

Research Organization:: Indiana Univ., Bloomington, IN (United States)

Sponsoring Organization:: Dept. of Navy; National Science Foundation; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-07ER15889

OSTI ID:: 1737556

Alternate ID(s):: OSTI ID: 1609794

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 10 Vol. 123; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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On the linear geometry of lanthanide hydroxide (Ln-OH, Ln = La–Lu) Harb, Hassan; Thompson, Lee M.; Hratchian, Hrant P. Physical Chemistry Chemical Physics, Vol. 21, Issue 39 https://doi.org/10.1039/c9cp01560d	journal	January 2019

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