The electronic structure of thorium monoxide: Ligand field assignment of states in the range 0–5 eV

Kaledin, Leonid A.; Kaledin, Alexey L.; Heaven, Michael C.

doi:10.1002/jcc.25710

Title: The electronic structure of thorium monoxide: Ligand field assignment of states in the range 0–5 eV

Journal Article · Wed Dec 12 00:00:00 EST 2018 · Journal of Computational Chemistry

DOI:https://doi.org/10.1002/jcc.25710· OSTI ID:1609348

Kaledin, Leonid A. ^[1]; Kaledin, Alexey L. ^[1];

^[1]

Emory Univ., Atlanta, GA (United States)

Configuration interaction ligand field theory (CI LFT) calculations of the electronic energy levels of ThO were performed by treating the molecular electronic states as Th ^{2 +} free‐ion levels perturbed by the ligand field of O ²⁻ . Twenty nine experimentally characterized ThO v = 0 energy levels, together with the energy difference between the v = 0 levels of the Y and W states were fitted using a CI LFT model that included Th ^{2 +} 7s ² , 6d7s, 6d ² , 7s7p, 6d7p, 5f7s, and 7p ² configurations. Predictions from these calculations were used to provide tentative assignments for 171 out of 250 ThO band heads listed by Gatterer et al. [“Molecular Spectra of Metallic Oxides”, Specola Vaticana (1957)]. Term energies for 30 electronic states have been determined based on these assignments. Subsequently, the CI LFT model was refined by fitting to a set of 59 electronic term energies. The inclusion of CI effects together with integer valence, atomic‐in‐molecule, ionic bonding ideas reveals atomic energy level patterns that are multiply replicated in the molecular energy level patterns of six Th ^{2 +} O ²⁻ atomic ion configurations (6d7s, 6d ² , 7s7p, 6d7p, 5f7s, and 7p ² ) revealing the underlying atomic ion structure that gives rise to the complex and seemingly erratic unassigned bands reported in the Vatican Atlas. © 2018 Wiley Periodicals, Inc.

View Accepted Manuscript (DOE)

View Accepted Manuscript (Publisher)

Cite

Export

Save

Research Organization:: Emory Univ., Atlanta, GA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: FG02-01ER15153; DE‐FG02‐01ER15153

OSTI ID:: 1609348

Alternate ID(s):: OSTI ID: 1485694

Journal Information:: Journal of Computational Chemistry, Vol. 40, Issue 2; ISSN 0192-8651

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 8 works

Citation information provided by
Web of Science

References (28)

An Algorithm for Least-Squares Estimation of Nonlinear Parameters Marquardt, Donald W. Journal of the Society for Industrial and Applied Mathematics, Vol. 11, Issue 2 https://doi.org/10.1137/0111030	journal	June 1963
Rotational Analysis of Yellow and Near Infrared Bands in ThO Edvinsson, G.; Lagerqvist, A. Physica Scripta, Vol. 30, Issue 5 https://doi.org/10.1088/0031-8949/30/5/005	journal	November 1984
Shot-noise-limited spin measurements in a pulsed molecular beam Kirilov, E.; Campbell, W. C.; Doyle, J. M. Physical Review A, Vol. 88, Issue 1 https://doi.org/10.1103/PhysRevA.88.013844	journal	July 2013
The Spectrum of ThO: Rotational Analysis of the L ¹ Π- X ¹ Σ ⁺ and N ¹ Π- X ¹ Σ ⁺ Systems Bornstedt, A. von; Edvinsson, G.; Lagerqvist, A. Physica Scripta, Vol. 20, Issue 5-6 https://doi.org/10.1088/0031-8949/20/5-6/007	journal	November 1979
Two new band systems in ThO Edvinsson, G.; Lagerqvist, A. Physica Scripta, Vol. 41, Issue 3 https://doi.org/10.1088/0031-8949/41/3/004	journal	March 1990
Probing the electronic structure of UO+ with high-resolution photoelectron spectroscopy Goncharov, Vasiliy; Kaledin, Leonid A.; Heaven, Michael C. The Journal of Chemical Physics, Vol. 125, Issue 13 https://doi.org/10.1063/1.2213262	journal	October 2006
The electronic structure of LaO: Ligand field versus ab initio calculations Schamps, Joël; Bencheikh, Mohammed; Barthelat, Jean‐Claude The Journal of Chemical Physics, Vol. 103, Issue 18 https://doi.org/10.1063/1.470219	journal	November 1995
Characterization of the $I (\| Ω \| = 1) - X^{1} Σ^{+} (0, 0)$ band of thorium oxide Kokkin, Damian L.; Steimle, Timothy C.; DeMille, David Physical Review A, Vol. 91, Issue 4 https://doi.org/10.1103/PhysRevA.91.042508	journal	April 2015
Low-Lying Levels in Certain Actinide Atoms Judd, B. R. Physical Review, Vol. 125, Issue 2 https://doi.org/10.1103/PhysRev.125.613	journal	January 1962
The 5 f ² -Configuration in Doubly Ionized Thorium, Th III Klinkenberg, P. F. A.; Uylings, P. H. M. Physica Scripta, Vol. 34, Issue 5 https://doi.org/10.1088/0031-8949/34/5/010	journal	November 1986
A low-lying state in the ThO molecule Edvinsson, Gunnar; Lagerqvist, Albin Journal of Molecular Spectroscopy, Vol. 113, Issue 1 https://doi.org/10.1016/0022-2852(85)90123-7	journal	September 1985
Energy‐adjusted pseudopotentials for the actinides. Parameter sets and test calculations for thorium and thorium monoxide Küchle, W.; Dolg, M.; Stoll, H. The Journal of Chemical Physics, Vol. 100, Issue 10 https://doi.org/10.1063/1.466847	journal	May 1994
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
The band spectrum of thorium oxide Edvinsson, G.; Selin, L. -E. Physics Letters, Vol. 9, Issue 3 https://doi.org/10.1016/0031-9163(64)90064-2	journal	April 1964
Ionization energy measurements and electronic spectra for ThO Goncharov, Vasiliy; Han, Jiande; Kaledin, Leonid A. The Journal of Chemical Physics, Vol. 122, Issue 20 https://doi.org/10.1063/1.1898222	journal	May 2005
The electronic structure of LaF: A multiconfiguration ligand field calculation Schall, Harold; Dulick, Michael; Field, Robert W. The Journal of Chemical Physics, Vol. 87, Issue 5 https://doi.org/10.1063/1.453078	journal	September 1987
Zur Deutung der Molekelspektren V: Die angeregten Elektronenterme von Molekeln mit zwei gleichen Kernen (H2, He2, Li2, N 2 + , N2 ...) Hund, F. Zeitschrift f�r Physik, Vol. 63, Issue 11-12 https://doi.org/10.1007/BF01339271	journal	November 1930
The permanent electric dipole moments and magnetic g factors of uranium monoxide Heaven, Michael C.; Goncharov, Vasiliy; Steimle, Timothy C. The Journal of Chemical Physics, Vol. 125, Issue 20 https://doi.org/10.1063/1.2378632	journal	November 2006
Spectra of Two Electron Systems Johnson, M. H. Physical Review, Vol. 38, Issue 9 https://doi.org/10.1103/PhysRev.38.1628	journal	November 1931
Extended Analysis of Doubly Ionized Thorium (Th III) Wyart, Jean-Francois; Kaufman, Victor Physica Scripta, Vol. 24, Issue 6 https://doi.org/10.1088/0031-8949/24/6/006	journal	December 1981
The Theory of Atomic Spectra Condon, E. U.; Shortley, G. H.; Ufford, C. W. American Journal of Physics, Vol. 20, Issue 6 https://doi.org/10.1119/1.1933256	journal	September 1952
Two band systems of ThO in the near ultraviolet Edvinsson, Gunnar; Lagerqvist, Albin Journal of Molecular Spectroscopy, Vol. 128, Issue 1 https://doi.org/10.1016/0022-2852(88)90211-1	journal	March 1988
Determination of the Ground State of ThIII Litzén, Ulf Physica Scripta, Vol. 10, Issue 1-2 https://doi.org/10.1088/0031-8949/10/1-2/009	journal	July 1974
Rotational analysis of some violet and green bands in the ThO spectrum Edvinsson, Gunnar; Lagerqvist, Albin Journal of Molecular Spectroscopy, Vol. 122, Issue 2 https://doi.org/10.1016/0022-2852(87)90017-8	journal	April 1987
Rotational Analysis of two Mutually Interacting Electronic States of ¹ Π Character in Th0 Bornstedt, A. von; Edvinsson, G. Physica Scripta, Vol. 2, Issue 4-5 https://doi.org/10.1088/0031-8949/2/4-5/012	journal	October 1970
Rotational Analysis of two Red Band Systems in the ThO Spectrum Edvinsson, G.; Lagerqvist, A. Physica Scripta, Vol. 32, Issue 6 https://doi.org/10.1088/0031-8949/32/6/007	journal	December 1985
Laser Spectroscopy of UO: Characterization and Assignment of States in the 0- to 3-eV Range, with a Comparison to the Electronic Structure of ThO Kaledin, L. A.; Mccord, J. E.; Heaven, M. C. Journal of Molecular Spectroscopy, Vol. 164, Issue 1 https://doi.org/10.1006/jmsp.1994.1055	journal	March 1994
The Electronic Structure of the Lanthanide Monohalides: A Ligand Field Approach Kaledin, Alexey L.; Heaven, Michael C.; Field, Robert W. Journal of Molecular Spectroscopy, Vol. 179, Issue 2 https://doi.org/10.1006/jmsp.1996.0209	journal	October 1996

Cited By (1)

The metastable Q ³ Δ ₂ state of ThO: a new resource for the ACME electron EDM search Wu, X.; Han, Z.; Chow, J. New Journal of Physics, Vol. 22, Issue 2 https://doi.org/10.1088/1367-2630/ab6a3a	journal	February 2020

Similar Records

The electronic structure of the actinide oxides and their singly and doubly charged cations: A ligand field approach

Journal Article · Mon Dec 21 00:00:00 EST 2020 · International Journal of Quantum Chemistry · OSTI ID:1609348

Kaledin, Leonid A.; Kaledin, Alexey L.; Heaven, Michael C.

Calculation of energy levels and transition amplitudes for barium and radium.

Journal Article · Mon Jan 01 00:00:00 EST 2007 · J. Phys. B · OSTI ID:1609348

Dzuba, V A; Flambaum, V V

Spectroscopic and theoretical studies of ThCl and ThCl⁺

Journal Article · Tue Feb 07 00:00:00 EST 2017 · Journal of Chemical Physics · OSTI ID:1609348

VanGundy, Robert A.; Bartlett, Joshua H.; Heaven, Michael C.; +2 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemistry

Title: The electronic structure of thorium monoxide: Ligand field assignment of states in the range 0–5 eV

Citation Formats

References (28)

Cited By (1)

Similar Records

Related Subjects