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

Title: Electronic and Molecular Structures of the CeB₆ Monomer

Journal Article · 20 February 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)

Cite

Export

Save

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

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

Grant/Contract Number:: FG02-07ER15889

OSTI ID:: 1737556

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

References (61)

PrB ₇ ⁻ : A Praseodymium-Doped Boron Cluster with a Pr ^II Center Coordinated by a Doubly Aromatic Planar η ⁷ -B ₇ ³⁻ Ligand Chen, Teng-Teng; Li, Wan-Lu; Jian, Tian Angewandte Chemie, Vol. 129, Issue 24 https://doi.org/10.1002/ange.201703111	journal	May 2017
Diatomic Molecule Electronic Structure beyond Simple Molecular Constants Field, Robert W. Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 86, Issue 9 https://doi.org/10.1002/bbpc.19820860903	journal	September 1982
Laser Spectroscopy of CeO: Characterization and Assignment of States in the 0-3 eV Range Kaledin, L. A.; Mccord, J. E.; Heaven, M. C. Journal of Molecular Spectroscopy, Vol. 158, Issue 1 https://doi.org/10.1006/jmsp.1993.1053	journal	March 1993
A spin correction procedure for unrestricted Hartree-Fock and Møller-Plesset wavefunctions for singlet diradicals and polyradicals Yamaguchi, K.; Jensen, F.; Dorigo, A. Chemical Physics Letters, Vol. 149, Issue 5-6 https://doi.org/10.1016/0009-2614(88)80378-6	journal	September 1988
Treatment of electronic excitations within the adiabatic approximation of time dependent density functional theory Bauernschmitt, Rüdiger; Ahlrichs, Reinhart Chemical Physics Letters, Vol. 256, Issue 4-5 https://doi.org/10.1016/0009-2614(96)00440-X	journal	July 1996
Electronic states of the CeO molecule: Absorption, emission, and laser spectroscopy Linton, C.; Dulick, M.; Field, R. W. Journal of Molecular Spectroscopy, Vol. 102, Issue 2 https://doi.org/10.1016/0022-2852(83)90053-X	journal	December 1983
Electronic structure of PrO: An analysis summary Dulick, M.; Field, R. W. Journal of Molecular Spectroscopy, Vol. 113, Issue 1 https://doi.org/10.1016/0022-2852(85)90124-9	journal	September 1985
High resolution analysis of transitions to the five lowest electronic states of samarium monoxide Bujin, Guo; Linton, C. Journal of Molecular Spectroscopy, Vol. 137, Issue 1 https://doi.org/10.1016/0022-2852(89)90273-7	journal	September 1989
The ultraviolet emission spectrum of LaO Carette, P. Journal of Molecular Spectroscopy, Vol. 140, Issue 2 https://doi.org/10.1016/0022-2852(90)90140-L	journal	April 1990
Laser spectroscopy of the lanthanide monofluorides: The ground state configuration of holmium fluoride Kaledin, L. A.; Linton, C.; Clarke, T. E. Journal of Molecular Spectroscopy, Vol. 154, Issue 2 https://doi.org/10.1016/0022-2852(92)90219-E	journal	August 1992
The magnetic and electrical properties of some rare earth tetraborides Etourneau, J.; Mercurio, J. P.; Berrada, A. Journal of the Less Common Metals, Vol. 67, Issue 2 https://doi.org/10.1016/0022-5088(79)90038-9	journal	October 1979
Elastic and magnetoelastic effects in CeB6 Lüthi, B.; Blumenröder, S.; Hillebrands, B. Journal of Magnetism and Magnetic Materials, Vol. 47-48 https://doi.org/10.1016/0304-8853(85)90429-9	journal	February 1985
Thermal conductivity of CeB6 and LaB6 Peysson, Y.; Ayache, C.; Salce, B. Journal of Magnetism and Magnetic Materials, Vol. 59, Issue 1-2 https://doi.org/10.1016/0304-8853(86)90007-7	journal	May 1986
Approximately spin-projected geometry optimization method and its application to di-chromium systems Kitagawa, Yasutaka; Saito, Toru; Ito, Masahide Chemical Physics Letters, Vol. 442, Issue 4-6 https://doi.org/10.1016/j.cplett.2007.05.082	journal	July 2007
Electronic structures of LaB6 and CeB6 single crystals: X-ray absorption near-edge structure studies at the B K-edge and the La and Ce giant resonance Liu, Lijia; Yiu, Yun-Mui; Sham, Tsun-Kong Journal of Electron Spectroscopy and Related Phenomena, Vol. 184, Issue 3-6 https://doi.org/10.1016/j.elspec.2011.03.002	journal	April 2011
Lanthanides with Unusually Low Oxidation States in the PrB ₃ ^– and PrB ₄ ^– Boride Clusters Chen, Xin; Chen, Teng-Teng; Li, Wan-Lu Inorganic Chemistry, Vol. 58, Issue 1 https://doi.org/10.1021/acs.inorgchem.8b02572	journal	December 2018
Modeling the Photoelectron Spectra of MoNbO ₂ ^– Accounting for Spin Contamination in Density Functional Theory Thompson, Lee M.; Hratchian, Hrant P. The Journal of Physical Chemistry A, Vol. 119, Issue 32 https://doi.org/10.1021/acs.jpca.5b04625	journal	August 2015
SmB ₆ ^– Cluster Anion: Covalency Involving f Orbitals Robinson, Paul J.; Zhang, Xinxing; McQueen, Tyrel The Journal of Physical Chemistry A, Vol. 121, Issue 8 https://doi.org/10.1021/acs.jpca.7b00247	journal	February 2017
A Tale of Two Stabilities: How One Boron Atom Affects a Switch in Bonding Motifs in CeO ₂ B _x ^– ( x = 2, 3) Complexes Mason, Jarrett L.; Harb, Hassan; Topolski, Josey E. The Journal of Physical Chemistry A, Vol. 122, Issue 51 https://doi.org/10.1021/acs.jpca.8b10446	journal	December 2018
Planarization of B ₇ ⁻ and B ₁₂ ⁻ Clusters by Isoelectronic Substitution: AlB ₆ ⁻ and AlB ₁₁ ⁻ Romanescu, Constantin; Sergeeva, Alina P.; Li, Wei-Li Journal of the American Chemical Society, Vol. 133, Issue 22 https://doi.org/10.1021/ja2012438	journal	June 2011
Structure and Bonding in B ₆ ^- and B ₆ : Planarity and Antiaromaticity Alexandrova, Anastassia N.; Boldyrev, Alexander I.; Zhai, Hua-Jin The Journal of Physical Chemistry A, Vol. 107, Issue 9 https://doi.org/10.1021/jp0268866	journal	March 2003
Study of MoNbO _y ( y = 2–5) Anion and Neutral Clusters Using Photoelectron Spectroscopy and Density Functional Theory Calculations: Impact of Spin Contamination on Single Point Calculations Waller, Sarah E.; Mann, Jennifer E.; Rothgeb, David W. The Journal of Physical Chemistry A, Vol. 116, Issue 39 https://doi.org/10.1021/jp306790z	journal	September 2012
Asymmetric Partitioning of Metals among Cluster Anions and Cations Generated via Laser Ablation of Mixed Aluminum/Group 6 Transition Metal Targets Waller, Sarah E.; Mann, Jennifer E.; Jarrold, Caroline Chick The Journal of Physical Chemistry A, Vol. 117, Issue 8 https://doi.org/10.1021/jp3119692	journal	February 2013
From planar boron clusters to borophenes and metalloborophenes Li, Wan-Lu; Chen, Xin; Jian, Tian Nature Reviews Chemistry, Vol. 1, Issue 10 https://doi.org/10.1038/s41570-017-0071	journal	September 2017
Observation of d–p hybridized aromaticity in lanthanum-doped boron clusters Cheng, Shi-Bo; Berkdemir, Cuneyt; Castleman, A. W. Phys. Chem. Chem. Phys., Vol. 16, Issue 2 https://doi.org/10.1039/C3CP53245C	journal	January 2014
[La(η ^x -B _x )La] ⁻ ( x = 7–9): a new class of inverse sandwich complexes Chen, Teng-Teng; Li, Wan-Lu; Li, Jun Chemical Science, Vol. 10, Issue 8 https://doi.org/10.1039/C8SC05443F	journal	January 2019
Probing actinide electronic structure using fluorescence and multi-photon ionization spectroscopy Heaven, Michael C. Physical Chemistry Chemical Physics, Vol. 8, Issue 39 https://doi.org/10.1039/b607486c	journal	January 2006
Valence basis sets for relativistic energy-consistent small-core lanthanide pseudopotentials Cao, Xiaoyan; Dolg, Michael The Journal of Chemical Physics, Vol. 115, Issue 16 https://doi.org/10.1063/1.1406535	journal	October 2001
Adiabatic time-dependent density functional methods for excited state properties Furche, Filipp; Ahlrichs, Reinhart The Journal of Chemical Physics, Vol. 117, Issue 16 https://doi.org/10.1063/1.1508368	journal	October 2002
Natural transition orbitals Martin, Richard L. The Journal of Chemical Physics, Vol. 118, Issue 11 https://doi.org/10.1063/1.1558471	journal	March 2003
Photoelectron spectroscopy and ab initio study of the doubly antiaromatic B62− dianion in the LiB6− cluster Alexandrova, Anastassia N.; Boldyrev, Alexander I.; Zhai, Hua-Jin The Journal of Chemical Physics, Vol. 122, Issue 5 https://doi.org/10.1063/1.1839575	journal	February 2005
Structures of Mo2Oy− and Mo2Oy (y=2, 3, and 4) studied by anion photoelectron spectroscopy and density functional theory calculations Yoder, Bruce L.; Maze, Joshua T.; Raghavachari, Krishnan The Journal of Chemical Physics, Vol. 122, Issue 9 https://doi.org/10.1063/1.1853379	journal	March 2005
Structures of trimetallic molybdenum and tungsten suboxide cluster anions Rothgeb, David W.; Mann, Jennifer E.; Waller, Sarah E. The Journal of Chemical Physics, Vol. 135, Issue 10 https://doi.org/10.1063/1.3635408	journal	September 2011
Self‐consistent molecular orbital methods. XVIII. Constraints and stability in Hartree–Fock theory Seeger, Rolf; Pople, John A. The Journal of Chemical Physics, Vol. 66, Issue 7 https://doi.org/10.1063/1.434318	journal	April 1977
Low lying electronic states of CeO Linton, C.; Dulick, M.; Field, R. W. The Journal of Chemical Physics, Vol. 74, Issue 1 https://doi.org/10.1063/1.440870	journal	January 1981
Laser production of supersonic metal cluster beams Dietz, T. G.; Duncan, M. A.; Powers, D. E. The Journal of Chemical Physics, Vol. 74, Issue 11 https://doi.org/10.1063/1.440991	journal	June 1981
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen Dunning, Thom H. The Journal of Chemical Physics, Vol. 90, Issue 2 https://doi.org/10.1063/1.456153	journal	January 1989
Vibrationally resolved photoelectron spectra of Si ⁻ ₃ and Si ⁻ ₄ Kitsopoulos, T. N.; Chick,, C. J.; Weaver, A. The Journal of Chemical Physics, Vol. 93, Issue 8 https://doi.org/10.1063/1.459004	journal	October 1990
Laser spectroscopy of low‐lying excited states in YbO: Linkage of the Yb ²⁺ f ¹³ s and f ¹⁴ configurations McDonald, Stephen A.; Rice, Steven F.; Field, Robert W. The Journal of Chemical Physics, Vol. 93, Issue 11 https://doi.org/10.1063/1.459347	journal	December 1990
Electronic structures of the negative ions Si ⁻ ₂ –Si ⁻ ₁₀ : Electron affinities of small silicon clusters Raghavachari, Krishnan; McMichael Rohlfing, Celeste The Journal of Chemical Physics, Vol. 94, Issue 5 https://doi.org/10.1063/1.459738	journal	March 1991
Threshold photodetachment spectroscopy of C ⁻ ₅ Kitsopoulos, T. N.; Chick, C. J.; Zhao, Y. The Journal of Chemical Physics, Vol. 95, Issue 7 https://doi.org/10.1063/1.461664	journal	October 1991
Stability analysis for solutions of the closed shell Kohn–Sham equation Bauernschmitt, Rüdiger; Ahlrichs, Reinhart The Journal of Chemical Physics, Vol. 104, Issue 22 https://doi.org/10.1063/1.471637	journal	June 1996
Study of the low-lying states of NiO− and NIO using anion photoelectron spectroscopy Moravec, Vicki D.; Jarrold, Caroline Chick The Journal of Chemical Physics, Vol. 108, Issue 5 https://doi.org/10.1063/1.475557	journal	February 1998
Communication: An efficient analytic gradient theory for approximate spin projection methods Hratchian, Hrant P. The Journal of Chemical Physics, Vol. 138, Issue 10 https://doi.org/10.1063/1.4795429	journal	March 2013
Hydrogen evolution from water through metal sulfide reactions Saha, Arjun; Raghavachari, Krishnan The Journal of Chemical Physics, Vol. 139, Issue 20 https://doi.org/10.1063/1.4830096	journal	November 2013
Second derivatives for approximate spin projection methods Thompson, Lee M.; Hratchian, Hrant P. The Journal of Chemical Physics, Vol. 142, Issue 5 https://doi.org/10.1063/1.4907269	journal	February 2015
Photoelectron spectra of CeO ⁻ and Ce(OH) ₂ ⁻ Ray, Manisha; Felton, Jeremy A.; Kafader, Jared O. The Journal of Chemical Physics, Vol. 142, Issue 6 https://doi.org/10.1063/1.4907714	journal	February 2015
Low-lying electronic structure of EuH, EuOH, and EuO neutrals and anions determined by anion photoelectron spectroscopy and DFT calculations Kafader, Jared O.; Ray, Manisha; Jarrold, Caroline Chick The Journal of Chemical Physics, Vol. 143, Issue 3 https://doi.org/10.1063/1.4926663	journal	July 2015
Photoelectron spectrum of PrO ⁻ Kafader, Jared O.; Ray, Manisha; Jarrold, Caroline Chick The Journal of Chemical Physics, Vol. 143, Issue 6 https://doi.org/10.1063/1.4928371	journal	August 2015
Natural ionization orbitals for interpreting electron detachment processes Thompson, Lee M.; Harb, Hassan; Hratchian, Hrant P. The Journal of Chemical Physics, Vol. 144, Issue 20 https://doi.org/10.1063/1.4951738	journal	May 2016
Insight into ethylene interactions with molybdenum suboxide cluster anions from photoelectron spectra of chemifragments Schaugaard, Richard N.; Topolski, Josey E.; Ray, Manisha The Journal of Chemical Physics, Vol. 148, Issue 5 https://doi.org/10.1063/1.5008264	journal	February 2018
Exotic electronic structures of Sm _x Ce _3−x O _y (x = 0-3; y = 2-4) clusters and the effect of high neutral density of low-lying states on photodetachment transition intensities Topolski, Josey E.; Kafader, Jared O.; Marrero-Colon, Vicmarie The Journal of Chemical Physics, Vol. 149, Issue 5 https://doi.org/10.1063/1.5043490	journal	August 2018
Observation of highly stable and symmetric lanthanide octa-boron inverse sandwich complexes Li, Wan-Lu; Chen, Teng-Teng; Xing, Deng-Hui Proceedings of the National Academy of Sciences, Vol. 115, Issue 30 https://doi.org/10.1073/pnas.1806476115	journal	July 2018
On approximate projection models Thompson, Lee M.; Hratchian, Hrant P. Molecular Physics, Vol. 117, Issue 9-12 https://doi.org/10.1080/00268976.2018.1554828	journal	December 2018
The electronic spectrum of gaseous CeO Barrow, R. F.; Clements, R. M.; Harris, S. M. The Astrophysical Journal, Vol. 229 https://doi.org/10.1086/156972	journal	April 1979
Elastic properties and electronic structures of lanthanide hexaborides Duan, Jie; Zhou, Tong; Zhang, Li Chinese Physics B, Vol. 24, Issue 9 https://doi.org/10.1088/1674-1056/24/9/096201	journal	September 2015
Photoelectron spectroscopy of GdO − Klingeler, R.; Pontius, N.; Lüttgens, G. Physical Review A, Vol. 65, Issue 3 https://doi.org/10.1103/PhysRevA.65.032502	journal	February 2002
Calculation of Ce − binding energies by analysis of photodetachment partial cross sections O’Malley, Steven M.; Beck, Donald R. Physical Review A, Vol. 74, Issue 4 https://doi.org/10.1103/PhysRevA.74.042509	journal	October 2006
Electronic structure and superconductivity in metal hexaborides Schell, G.; Winter, H.; Rietschel, H. Physical Review B, Vol. 25, Issue 3 https://doi.org/10.1103/PhysRevB.25.1589	journal	February 1982
5 d and 4 f electron configuration of CeB ₆ at 340 and 535 K Makita, Ryoko; Tanaka, Kiyoaki; Ōnuki, Yoshichika Acta Crystallographica Section B Structural Science, Vol. 64, Issue 5 https://doi.org/10.1107/S0108768108026542	journal	September 2008
Dye laser and thermal emission spectroscopy of the TbO molecule Kulikov, N.; Kaledin, L. A.; Kobyliansky, A. I. Canadian Journal of Physics, Vol. 62, Issue 12 https://doi.org/10.1139/p84-229	journal	December 1984

Cited By (1)

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

Similar Records

Low-lying electronic structure of EuH, EuOH, and EuO neutrals and anions determined by anion photoelectron spectroscopy and DFT calculations

Journal Article · 2015 · Journal of Chemical Physics · OSTI ID:22490916

Kafader, Jared O.; Ray, Manisha

Exceptionally Complex Electronic Structures of Lanthanide Oxides and Small Molecules

Journal Article · 2019 · Accounts of Chemical Research · OSTI ID:1737549

Mason, Jarrett L.; Harb, Hassan; Topolski, Josey E.; +2 more

Photoelectron spectra of CeO{sup −} and Ce(OH){sub 2}{sup −}

Journal Article · 2015 · Journal of Chemical Physics · OSTI ID:22410271

Ray, Manisha; Felton, Jeremy A.; Kafader, Jared O.; +1 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Anions
Chemical structure
Electrical energy
Electronic structure
Molecular structure

Title: Electronic and Molecular Structures of the CeB6 Monomer

Citation Formats

References (61)

Cited By (1)

Similar Records

Related Subjects

Title: Electronic and Molecular Structures of the CeB₆ Monomer