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

Abstract

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, 6dmore » 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.« less

Authors:

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

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+ Show Author Affiliations

1. Emory Univ., Atlanta, GA (United States)

Publication Date:

Wed Dec 12 00:00:00 EST 2018

Research Org.:

Emory Univ., Atlanta, GA (United States)

Sponsoring Org.:

USDOE Office of Science (SC)

OSTI Identifier:

1609348

Alternate Identifier(s):

OSTI ID: 1485694

Grant/Contract Number:  

FG02-01ER15153; DE‐FG02‐01ER15153

Resource Type:

Accepted Manuscript

Journal Name:

Journal of Computational Chemistry

Additional Journal Information:

Journal Volume: 40; Journal Issue: 2; Journal ID: ISSN 0192-8651

Publisher:

Wiley

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry