skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Theoretical spectroscopy study of the low-lying electronic states of UX and UX+, X = F and Cl

Abstract

Spectroscopic constants (Te, re, B0, ωe, ωexe) have been calculated for the low-lying electronic states of UF, UF+, UCl, and UCl+ using complete active space 2nd-order perturbation theory (CASPT2), with a series of correlation consistent basis sets. The latter included those based on both pseudopotential (PP) and all-electron Douglas-Kroll-Hess (DK) Hamiltonians for the U atom. Spin orbit effects were included a posteri using the state interacting method using both PP and Breit Pauli (BP) operators, as well as from exact two-component (X2C) methods for U+ and UF+. Complete basis set (CBS) limits were obtained by extrapolation where possible and the PP and BP calculations were compared at their respective CBS limits. The PP-based method was shown to be reliable in calculating spectroscopic constants, in particular when using the state interacting method with CASPT2 energies (SO-CASPT2). The two component calculations were limited by computational resources and could not include electron correlation from the nominally closed shell 6s and 6p orbitals of U. UF and UCl were both calculated to have Ω=9/2 ground states. The first excited state of UCl was calculated to be an Ω=7/2 state at 78 cm-1 as opposed to the same state at 435 cm-1 in UF, andmore » the other low-lying states of UCl showed a similar compression relative to UF. Likewise UF+ and UCl+ both have Ω=4 ground states and the manifold of low-lying excited Ω = 3, 2, 1, 0 states were energetically closer together in UCl+ than in UF+, ranging up to 776 cm-1 in UF+ and only 438 cm-1 in UCl+. As in previous research, the final PP-based SO-CASPT2 results for UF+ and UF agree well with experiment, and are expected to be predictive for UCl and UCl+, which are reported here for the first time.« less

Authors:
 [1]; ORCiD logo [1]
  1. Washington State Univ., Pullman, WA (United States)
Publication Date:
Research Org.:
Washington State Univ., Pullman, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1224465
Alternate Identifier(s):
OSTI ID: 1225988
Grant/Contract Number:  
SC0008501; FG02-12ER16329
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 143; Journal Issue: 18; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; UF; UCl; uranium halides; uranium halide cations; ab initio; ground states; excitation energies; spin orbit interactions; electron correlation calculations; electron spectroscopy

Citation Formats

Bross, David H., and Peterson, Kirk A. Theoretical spectroscopy study of the low-lying electronic states of UX and UX+, X = F and Cl. United States: N. p., 2015. Web. doi:10.1063/1.4935492.
Bross, David H., & Peterson, Kirk A. Theoretical spectroscopy study of the low-lying electronic states of UX and UX+, X = F and Cl. United States. doi:10.1063/1.4935492.
Bross, David H., and Peterson, Kirk A. Fri . "Theoretical spectroscopy study of the low-lying electronic states of UX and UX+, X = F and Cl". United States. doi:10.1063/1.4935492. https://www.osti.gov/servlets/purl/1224465.
@article{osti_1224465,
title = {Theoretical spectroscopy study of the low-lying electronic states of UX and UX+, X = F and Cl},
author = {Bross, David H. and Peterson, Kirk A.},
abstractNote = {Spectroscopic constants (Te, re, B0, ωe, ωexe) have been calculated for the low-lying electronic states of UF, UF+, UCl, and UCl+ using complete active space 2nd-order perturbation theory (CASPT2), with a series of correlation consistent basis sets. The latter included those based on both pseudopotential (PP) and all-electron Douglas-Kroll-Hess (DK) Hamiltonians for the U atom. Spin orbit effects were included a posteri using the state interacting method using both PP and Breit Pauli (BP) operators, as well as from exact two-component (X2C) methods for U+ and UF+. Complete basis set (CBS) limits were obtained by extrapolation where possible and the PP and BP calculations were compared at their respective CBS limits. The PP-based method was shown to be reliable in calculating spectroscopic constants, in particular when using the state interacting method with CASPT2 energies (SO-CASPT2). The two component calculations were limited by computational resources and could not include electron correlation from the nominally closed shell 6s and 6p orbitals of U. UF and UCl were both calculated to have Ω=9/2 ground states. The first excited state of UCl was calculated to be an Ω=7/2 state at 78 cm-1 as opposed to the same state at 435 cm-1 in UF, and the other low-lying states of UCl showed a similar compression relative to UF. Likewise UF+ and UCl+ both have Ω=4 ground states and the manifold of low-lying excited Ω = 3, 2, 1, 0 states were energetically closer together in UCl+ than in UF+, ranging up to 776 cm-1 in UF+ and only 438 cm-1 in UCl+. As in previous research, the final PP-based SO-CASPT2 results for UF+ and UF agree well with experiment, and are expected to be predictive for UCl and UCl+, which are reported here for the first time.},
doi = {10.1063/1.4935492},
journal = {Journal of Chemical Physics},
number = 18,
volume = 143,
place = {United States},
year = {2015},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Save / Share:

Works referenced in this record:

Handbook of Basic Atomic Spectroscopic Data
journal, December 2005

  • Sansonetti, J. E.; Martin, W. C.
  • Journal of Physical and Chemical Reference Data, Vol. 34, Issue 4
  • DOI: 10.1063/1.1800011

An efficient second-order MC SCF method for long configuration expansions
journal, April 1985


Spectroscopy and Structure of the Simplest Actinide Bonds
journal, October 2014

  • Heaven, Michael C.; Barker, Beau J.; Antonov, Ivan O.
  • The Journal of Physical Chemistry A, Vol. 118, Issue 46
  • DOI: 10.1021/jp507283n

On the effectiveness of CCSD(T) complete basis set extrapolations for atomization energies
journal, July 2011

  • Feller, David; Peterson, Kirk A.; Grant Hill, J.
  • The Journal of Chemical Physics, Vol. 135, Issue 4
  • DOI: 10.1063/1.3613639

Probing the electronic structure of UO+ with high-resolution photoelectron spectroscopy
journal, October 2006

  • Goncharov, Vasiliy; Kaledin, Leonid A.; Heaven, Michael C.
  • The Journal of Chemical Physics, Vol. 125, Issue 13
  • DOI: 10.1063/1.2213262

Relativistic Hamiltonians for Chemistry: A Primer
journal, November 2011


Multireference perturbation theory for large restricted and selected active space reference wave functions
journal, April 2000

  • Celani, Paolo; Werner, Hans-Joachim
  • The Journal of Chemical Physics, Vol. 112, Issue 13
  • DOI: 10.1063/1.481132

How accurate are electronic structure methods for actinoid chemistry?
journal, March 2011

  • Averkiev, Boris B.; Mantina, Manjeera; Valero, Rosendo
  • Theoretical Chemistry Accounts, Vol. 129, Issue 3-5
  • DOI: 10.1007/s00214-011-0913-0

New spectroscopic data on high-lying excited levels of atomic uranium
journal, January 1982

  • Coste, A.; Avril, R.; Blancard, P.
  • Journal of the Optical Society of America, Vol. 72, Issue 1
  • DOI: 10.1364/josa.72.000103

Ab initio total atomization energies of small molecules — towards the basis set limit
journal, September 1996


Stark and Zeeman effect in the [18.6]3.5 – X(1)4.5 transition of uranium monofluoride, UF
journal, June 2014

  • Linton, C.; Adam, A. G.; Steimle, T. C.
  • The Journal of Chemical Physics, Vol. 140, Issue 21
  • DOI: 10.1063/1.4880255

Composite thermochemistry of gas phase U(VI)-containing molecules
journal, December 2014

  • Bross, David H.; Peterson, Kirk A.
  • The Journal of Chemical Physics, Vol. 141, Issue 24
  • DOI: 10.1063/1.4904721

Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
journal, January 1989

  • Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 90, Issue 2
  • DOI: 10.1063/1.456153

Benchmarking Electronic Structure Calculations on the Bare UO 2 2+ Ion: How Different are Single and Multireference Electron Correlation Methods?
journal, November 2009

  • Réal, Florent; Gomes, André Severo Pereira; Visscher, Lucas
  • The Journal of Physical Chemistry A, Vol. 113, Issue 45
  • DOI: 10.1021/jp903758c

Correlation consistent basis sets for actinides. I. The Th and U atoms
journal, February 2015

  • Peterson, Kirk A.
  • The Journal of Chemical Physics, Vol. 142, Issue 7
  • DOI: 10.1063/1.4907596

Diatomic Molecule Electronic Structure beyond Simple Molecular Constants
journal, September 1982

  • Field, Robert W.
  • Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 86, Issue 9
  • DOI: 10.1002/bbpc.19820860903

Electronic Spectroscopy of UO
journal, September 1997

  • Kaledin, Leonid A.; Heaven, Michael C.
  • Journal of Molecular Spectroscopy, Vol. 185, Issue 1
  • DOI: 10.1006/jmsp.1997.7383

Quantum Chemical Calculations and Experimental Investigations of Molecular Actinide Oxides
journal, January 2015

  • Kovács, Attila; Konings, Rudy J. M.; Gibson, John K.
  • Chemical Reviews, Vol. 115, Issue 4
  • DOI: 10.1021/cr500426s

Accurate correlation consistent basis sets for molecular core–valence correlation effects: The second row atoms Al–Ar, and the first row atoms B–Ne revisited
journal, December 2002

  • Peterson, Kirk A.; Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 117, Issue 23
  • DOI: 10.1063/1.1520138

All-Electron Scalar Relativistic Basis Sets for the Actinides
journal, February 2011

  • Pantazis, Dimitrios A.; Neese, Frank
  • Journal of Chemical Theory and Computation, Vol. 7, Issue 3
  • DOI: 10.1021/ct100736b

Theoretical study on ThF + , a prospective system in search of time-reversal violation
journal, April 2015


An infinite-order two-component relativistic Hamiltonian by a simple one-step transformation
journal, February 2007

  • Iliaš, Miroslav; Saue, Trond
  • The Journal of Chemical Physics, Vol. 126, Issue 6
  • DOI: 10.1063/1.2436882

An efficient internally contracted multiconfiguration–reference configuration interaction method
journal, November 1988

  • Werner, Hans‐Joachim; Knowles, Peter J.
  • The Journal of Chemical Physics, Vol. 89, Issue 9
  • DOI: 10.1063/1.455556

All-electron Douglas–Kroll–Hess and pseudopotential study on the low-lying states of uranium hydride UH
journal, January 2008


A modified definition of the zeroth-order Hamiltonian in multiconfigurational perturbation theory (CASPT2)
journal, September 2004


Gaussian basis sets for use in correlated molecular calculations. III. The atoms aluminum through argon
journal, January 1993

  • Woon, David E.; Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 98, Issue 2
  • DOI: 10.1063/1.464303

Internally contracted multiconfiguration-reference configuration interaction calculations for excited states
journal, October 1992

  • Knowles, Peter J.; Werner, Hans-Joachim
  • Theoretica Chimica Acta, Vol. 84, Issue 1-2
  • DOI: 10.1007/bf01117405

Comment on: “Estimating the Hartree–Fock limit from finite basis set calculations” [Jensen F (2005) Theor Chem Acc 113:267]
journal, December 2005


Relativistic Pseudopotentials: Their Development and Scope of Applications
journal, September 2011

  • Dolg, Michael; Cao, Xiaoyan
  • Chemical Reviews, Vol. 112, Issue 1
  • DOI: 10.1021/cr2001383

All-Electron Hybrid Density Functional Calculations on UF n and UCl n ( n = 1−6)
journal, May 2005

  • Peralta, Juan E.; Batista, Enrique R.; Scuseria, Gustavo E.
  • Journal of Chemical Theory and Computation, Vol. 1, Issue 4
  • DOI: 10.1021/ct050047g

Parallel Douglas–Kroll energy and gradients in NWChem: Estimating scalar relativistic effects using Douglas–Kroll contracted basis sets
journal, January 2001

  • de Jong, W. A.; Harrison, R. J.; Dixon, D. A.
  • The Journal of Chemical Physics, Vol. 114, Issue 1
  • DOI: 10.1063/1.1329891

Spin-orbit matrix elements for internally contracted multireference configuration interaction wavefunctions
journal, November 2000

  • Berning, Andreas; Schweizer, Marcus; Werner, Hans-Joachim
  • Molecular Physics, Vol. 98, Issue 21
  • DOI: 10.1080/00268970009483386

A second order multiconfiguration SCF procedure with optimum convergence
journal, June 1985

  • Werner, Hans‐Joachim; Knowles, Peter J.
  • The Journal of Chemical Physics, Vol. 82, Issue 11
  • DOI: 10.1063/1.448627

Gaussian basis sets for use in correlated molecular calculations. X. The atoms aluminum through argon revisited
journal, June 2001

  • Dunning, Thom H.; Peterson, Kirk A.; Wilson, Angela K.
  • The Journal of Chemical Physics, Vol. 114, Issue 21
  • DOI: 10.1063/1.1367373

The Energy Levels of a Rotating Vibrator
journal, September 1932


A Fock space coupled cluster study on the electronic structure of the UO2, UO2+, U4+, and U5+ species
journal, September 2007

  • Infante, Ivan; Eliav, Ephraim; Vilkas, Marius J.
  • The Journal of Chemical Physics, Vol. 127, Issue 12
  • DOI: 10.1063/1.2770699

Electronic structure of UH, UF, and their ions
journal, July 1983

  • Krauss, M.; Stevens, W. J.
  • Journal of Computational Chemistry, Vol. 4, Issue 2
  • DOI: 10.1002/jcc.540040202

Spectroscopic and Theoretical Investigations of UF and UF +
journal, February 2013

  • Antonov, Ivan O.; Heaven, Michael C.
  • The Journal of Physical Chemistry A, Vol. 117, Issue 39
  • DOI: 10.1021/jp312362e

An ab initio study of excited states of U and UF
journal, March 2003

  • Fedorov, Dmitri G.; Nakajima, Takahito; Hirao, Kimihiko
  • The Journal of Chemical Physics, Vol. 118, Issue 11
  • DOI: 10.1063/1.1545105

Reactions of Laser-Ablated U Atoms with HF: Infrared Spectra and Quantum Chemical Calculations of HUF, UH, and UF in Noble Gas Solids
journal, August 2014

  • Vent-Schmidt, Thomas; Andrews, Lester; Riedel, Sebastian
  • The Journal of Physical Chemistry A, Vol. 119, Issue 11
  • DOI: 10.1021/jp5055827

Actinide speciation in the environment
journal, January 2003


An efficient method for the evaluation of coupling coefficients in configuration interaction calculations
journal, April 1988


Accurate Relativistic Small-Core Pseudopotentials for Actinides. Energy Adjustment for Uranium and First Applications to Uranium Hydride
journal, November 2009

  • Dolg, Michael; Cao, Xiaoyan
  • The Journal of Physical Chemistry A, Vol. 113, Issue 45
  • DOI: 10.1021/jp9044594

Third-order multireference perturbation theory The CASPT3 method
journal, October 1996


Actinide speciation in the environment
journal, June 2007


Internally contracted multiconfiguration-reference configuration interaction calculations for excited states
journal, October 1992

  • Knowles, Peter J.; Werner, Hans-Joachim
  • Theoretica Chimica Acta, Vol. 84, Issue 1-2
  • DOI: 10.1007/BF01117405

Third-order multireference perturbation theory The CASPT3 method
journal, October 1996


The Energy Levels of a Rotating Vibrator
journal, September 1932


New spectroscopic data on high-lying excited levels of atomic uranium
journal, January 1982

  • Coste, A.; Avril, R.; Blancard, P.
  • Journal of the Optical Society of America, Vol. 72, Issue 1
  • DOI: 10.1364/JOSA.72.000103

    Works referencing / citing this record:

    Correlation consistent basis sets for lanthanides: The atoms La–Lu
    journal, August 2016

    • Lu, Qing; Peterson, Kirk A.
    • The Journal of Chemical Physics, Vol. 145, Issue 5
    • DOI: 10.1063/1.4959280

    Spectroscopic and theoretical studies of ThCl and ThCl +
    journal, February 2017

    • VanGundy, Robert A.; Bartlett, Joshua H.; Heaven, Michael C.
    • The Journal of Chemical Physics, Vol. 146, Issue 5
    • DOI: 10.1063/1.4975070