Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Optical Stark and Zeeman Spectroscopy of Thorium Fluoride, ThF, and Thorium Chloride, ThCl

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
 [1];  [2];  [3];  [4]
  1. Arizona State Univ., Tempe, AZ (United States). School of Molecular Sciences; School of Molecular sciences Arizona State University
  2. Arizona State Univ., Tempe, AZ (United States). School of Molecular Sciences
  3. Univ. of New Brunswick, Fredericton, NB (Canada). Physics Dept.
  4. Johns Hopkins Univ., Baltimore, MD (United States). Dept. of Chemistry
+ Show Author Affiliations
Experimentally and theoretically determined magnetic and electric dipole moments, bond distances and vibrational spacings are used for a comparative study of the bonding in ThF and ThCl. Numerous bands in the visible electronic spectra between 16400 cm-1-18800 cm-1 of supersonically cooled molecular beam samples have been detected using medium resolution (Δν≈ 0.1cm-1), two dimensional (2D) spectroscopy. High resolution (Δν < 20 MHz) field-free, Stark, and Zeeman spectroscopy of the detected [18.6] Ω=3/2 – X2Δ3/2 band of ThF near 538.4 nm and the [18.2] Ω=3/2 – X2Δ3/2 band of ThCl near 551.0 nm have been recorded and analyzed. Stark shifts and splitting were analyzed to produce |rμel| values of 1.453(7) D and 0.588(9) D, for the X2Δ3/2 and [18.6]Ω=3/2 states of ThF, respectively, and 2.022(35) D and 3.020(55) D, for the X2Δ3/2 and [18.2]Ω=3/2 states of ThCl. Zeeman splittings and shifts were analyzed to produce ge values of 1.038(4) and 1.079(4) for the X2Δ3/2 and [18.6]Ω=3/2 states of ThF and 1.130(4) and 1.638(4) for the X2Δ3/2 and [18.2]Ω=3/2 states of ThCl. Analysis of ge values demonstrate that the X2Δ3/2 and [18.6]Ω=3/2 states of ThF and the X2Δ3/2 state of ThCl are predominately 2Δ3/2 spin-orbit components, whereas the [18.2] Ω=3/2 state of ThCl is an admixture of 2Δ3/2 and 2Π3/2 spin-orbit components. A molecular orbital description of the ground states is used to rationalize the observed |rμel| values for the ThX(X=F,Cl,O and S) series, and garner insight into the bonding mechanism. The dipole moments in the ground state of ThF and ThCl have been calculated using relativistic coupled-cluster methods. It is demonstrated that the systematic inclusion of electron-correlation contributions plays an essential role in obtaining accurate predictions for the dipole-moment values in ThF and ThCl.
Research Organization:
Arizona State Univ., Tempe, AZ (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0018241
OSTI ID:
1491862
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: 7 Vol. 123; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (50)

Diatomic Molecule Electronic Structure beyond Simple Molecular Constants journal September 1982
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 journal March 1994
Relativistic calculations on thallium hydride journal January 2001
A new implementation of the full CCSDT model for molecular electronic structure journal November 1988
A mean-field spin-orbit method applicable to correlated wavefunctions journal March 1996
Λ-Type doubling parameters for molecules in Δ electronic states journal August 1987
A fifth-order perturbation comparison of electron correlation theories journal May 1989
The pure rotational spectrum of thorium monosulfide, ThS journal October 2015
Rotational Spectroscopy of Diatomic Molecules book January 2003
Ab Initio Ligand-Field Theory Analysis and Covalency Trends in Actinide and Lanthanide Free Ions and Octahedral Complexes journal July 2017
Correction to Spectroscopy and Structure of the Simplest Actinide Bonds journal October 2015
Insight into the Extraction Mechanism of Americium(III) over Europium(III) with Pyridylpyrazole: A Relativistic Quantum Chemistry Study journal April 2018
Coordination Chemistry with f-Element Complexes for an Improved Understanding of Factors That Contribute to Extraction Selectivity journal June 2012
New Relativistic ANO Basis Sets for Transition Metal Atoms journal July 2005
Two-Dimensional Fluorescence (Excitation/Emission) Spectroscopy as a Probe of Complex Chemical Environments journal November 2006
Gas-Phase Energetics of Thorium Fluorides and Their Ions journal October 2012
Properties of ThF x from Infrared Spectra in Solid Argon and Neon with Supporting Electronic Structure and Thermochemical Calculations journal March 2014
Spectroscopy and Structure of the Simplest Actinide Bonds journal October 2014
Extraction of minor actinides, lanthanides and other fission products by silica-immobilized BTBP/BTPhen ligands journal January 2017
Understanding Am 3+ /Cm 3+ separation with H 4 TPAEN and its hydrophilic derivatives: a quantum chemical study journal January 2018
Ligands for f-element extraction used in the nuclear fuel cycle journal January 2017
The pure rotational spectrum of the actinide-containing compound thorium monoxide journal January 2007
Higher excitations in coupled-cluster theory journal August 2001
Interfacing relativistic and nonrelativistic methods. IV. One- and two-electron scalar approximations journal November 2001
Coupled-cluster methods including noniterative corrections for quadruple excitations journal August 2005
Approximate treatment of higher excitations in coupled-cluster theory journal December 2005
Response to “Comment on ‘Quasirelativistic theory equivalent to fully relativistic theory’ ” [J. Chem. Phys. 123, 241102 (2005)] journal September 2006
The permanent electric dipole moments and magnetic g factors of uranium monoxide journal November 2006
An infinite-order two-component relativistic Hamiltonian by a simple one-step transformation journal February 2007
Exact two-component Hamiltonians revisited journal July 2009
Two dimensional laser induced fluorescence spectroscopy: A powerful technique for elucidating rovibronic structure in electronic transitions of polyatomic molecules journal May 2011
Analytic energy gradients for the spin-free exact two-component theory using an exact block diagonalization for the one-electron Dirac Hamiltonian journal August 2011
Spectroscopic investigations of ThF and ThF + journal March 2012
Sub‐Doppler Zeeman spectroscopy of the CeO molecule journal July 1986
The full CCSDT model for molecular electronic structure journal June 1987
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen journal January 1989
A direct product decomposition approach for symmetry exploitation in many‐body methods. I. Energy calculations journal March 1991
Coupled‐cluster methods with noniterative triple excitations for restricted open‐shell Hartree–Fock and other general single determinant reference functions. Energies and analytical gradients journal June 1993
Interfacing relativistic and nonrelativistic methods. I. Normalized elimination of the small component in the modified Dirac equation journal June 1997
Optical Zeeman spectroscopy of the (0,0) B 4 Γ – X 4 Φ band systems of titanium monohydride, TiH, and titanium monodeuteride, TiD journal August 2012
Resonant two-photon ionization spectroscopy of jet-cooled UN: Determination of the ground state journal May 2013
The permanent electric dipole moment of thorium sulfide, ThS journal January 2014
Stark and Zeeman effect in the [18.6]3.5 – X(1)4.5 transition of uranium monofluoride, UF journal June 2014
Theoretical spectroscopy study of the low-lying electronic states of UX and UX+, X = F and Cl journal November 2015
Spectroscopic and theoretical studies of ThCl and ThCl + journal February 2017
Correlation consistent basis sets for actinides. II. The atoms Ac and Np–Lr journal August 2017
Two-component relativistic coupled-cluster methods using mean-field spin-orbit integrals journal January 2018
An atomic mean-field spin-orbit approach within exact two-component theory for a non-perturbative treatment of spin-orbit coupling journal April 2018
Branching ratios and radiative lifetimes of the U , L , and I states of thorium oxide journal December 2014
Characterization of the I ( | Ω | = 1 ) – X 1 Σ + ( 0 , 0 ) band of thorium oxide journal April 2015

Cited By (2)

The Chronus Quantum software package journal August 2019
Characterization of gas-phase thorium nitride journal April 2019

Similar Records

Stark and Zeeman effect in the [18.6]3.5 – X(1)4.5 transition of uranium monofluoride, UF
Journal Article · Sat Jun 07 00:00:00 EDT 2014 · Journal of Chemical Physics · OSTI ID:22304265
The electric dipole moment of cobalt monoxide, CoO
Journal Article · Fri Mar 28 00:00:00 EDT 2014 · Journal of Chemical Physics · OSTI ID:22253397
Characterization of gas-phase thorium nitride
Journal Article · Mon Apr 08 20:00:00 EDT 2019 · Journal of Chemical Physics · OSTI ID:1609350

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY