Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Correlation consistent basis sets for actinides. II. The atoms Ac and Np–Lr

Journal Article · · Journal of Chemical Physics
DOI: https://doi.org/10.1063/1.4994725 · OSTI ID:1535331
 [1]; ORCiD logo [2]
  1. Washington State Univ., Pullman, WA (United States); DOE/OSTI
  2. Washington State Univ., Pullman, WA (United States)
+ Show Author Affiliations

New correlation consistent basis sets optimized using the all-electron third-order Douglas-Kroll-Hess (DKH3) scalar relativistic Hamiltonian are reported for the actinide elements Ac and Np through Lr. These complete the series of sets reported previously for Th–U [K. A. Peterson, J. Chem. Phys. 142, 074105 (2015); M. Vasiliu et al., J. Phys. Chem. A 119, 11422 (2015)]. The new sets range in size from double- to quadruple-zeta and encompass both those optimized for valence (6s6p5f7s6d) and outer-core electron correlations (valence + 5s5p5d). The final sets have been contracted for both the DKH3 and eXact 2-component (X2C) Hamiltonians, yielding cc-pVnZ-DK3/cc-pVnZ-X2C sets for valence correlation and cc-pwCVnZ-DK3/cc-pwCVnZ-X2C sets for outer-core correlation (n = D, T, Q in each case). In order to test the effectiveness of the new basis sets, both atomic and molecular benchmark calculations have been carried out. In the first case, the first three atomic ionization potentials (IPs) of all the actinide elements Ac–Lr have been calculated using the Feller-Peterson-Dixon (FPD) composite approach, primarily with the multireference configuration interaction (MRCI) method. Excellent convergence towards the respective complete basis set (CBS) limits is achieved with the new sets, leading to good agreement with experiment, where these exist, after accurately accounting for spin-orbit effects using the 4-component Dirac-Hartree-Fock method. For a molecular test, the IP and atomization energy (AE) of PuO2 have been calculated also using the FPD method but using a coupled cluster approach with spin-orbit coupling accounted for using the 4-component MRCI. The present calculations yield an IP0 for PuO2 of 159.8 kcal/mol, which is in excellent agreement with the experimental electron transfer bracketing value of 162 ± 3 kcal/mol. Likewise, the calculated 0 K AE of 305.6 kcal/mol is in very good agreement with the currently accepted experimental value of 303.1 ± 5 kcal/mol. The ground state of PuO2 is predicted to be the 5Σ$$+\atop{0g}$$ state.

Research Organization:
Washington State Univ., Pullman, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
SC0008501
OSTI ID:
1535331
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 8 Vol. 147; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

References (68)

Gaussian Basis Sets for Lanthanide and Actinide Elements book January 2015
Controversy on the First Ionization Potential of PuO2 (Nearly) Settled by New Experimental Evidence. journal March 2006
Configuration interaction calculations on the nitrogen molecule journal January 1974
A diagnostic for determining the quality of single-reference electron correlation methods journal April 1989
Molpro: a general-purpose quantum chemistry program package: Molpro
  • Werner, Hans-Joachim; Knowles, Peter J.; Knizia, Gerald
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 2 https://doi.org/10.1002/wcms.82
journal July 2011
Spectra and Electronic Structures of Free Actinide Atoms and Ions book January 2006
Comment on: “Estimating the Hartree–Fock limit from finite basis set calculations” [Jensen F (2005) Theor Chem Acc 113:267] journal December 2005
Relativistic double-zeta, triple-zeta, and quadruple-zeta basis sets for the actinides Ac–Lr journal October 2006
Chemical accuracy in ab initio thermochemistry and spectroscopy: current strategies and future challenges journal January 2012
Correlation consistent, Douglas–Kroll–Hess relativistic basis sets for the 5p and 6p elements journal December 2013
Relativistic Gaussian basis sets for the elements K - Uuo journal January 2001
Quantum electrodynamical corrections to the fine structure of helium journal January 1974
An efficient method for the evaluation of coupling coefficients in configuration interaction calculations journal April 1988
Passing the one-billion limit in full configuration-interaction (FCI) calculations journal June 1990
The open-shell restricted Hartree—Fock singles and doubles coupled-cluster method including triple excitations CCSD (T): application to C+3 journal January 1991
Ab initio total atomization energies of small molecules — towards the basis set limit journal September 1996
A Practical Guide to Reliable First Principles Computational Thermochemistry Predictions Across the Periodic Table book January 2012
New relativistic ANO basis sets for actinide atoms journal June 2005
A fifth-order perturbation comparison of electron correlation theories journal May 1989
An ab initio study of PuO2 and of PuN2 journal September 2000
Use of Improved Orbitals for CCSD(T) Calculations for Predicting Heats of Formation of Group IV and Group VI Metal Oxide Monomers and Dimers and UCl 6 journal July 2016
Reliable Potential Energy Surfaces for the Reactions of H 2 O with ThO 2 , PaO 2 + , UO 2 2+ , and UO 2 + journal November 2015
Quantum Chemical Calculations and Experimental Investigations of Molecular Actinide Oxides journal January 2015
All-Electron Scalar Relativistic Basis Sets for the Actinides journal February 2011
Gas-Phase Oxidation Reactions of Neptunium and Plutonium Ions Investigated via Fourier Transform Ion Cyclotron Resonance Mass Spectrometry journal August 2002
Controversy on the First Ionization Potential of PuO 2 (Nearly) Settled by New Experimental Evidence journal December 2005
Ionization Energies for the Actinide Mono- and Dioxides Series, from Th to Cm: Theory versus Experiment journal May 2010
Relativistic Small-Core Pseudopotentials for Actinium, Thorium, and Protactinium journal March 2014
Mass Spectrometric Measurement Of the Ionization Energies and Cross Sections Of Uranium and Plutonium Oxide Vapors journal December 1999
Measurement of the first ionization potential of lawrencium, element 103 journal April 2015
A theoretical study of the ground state and lowest excited states of PuO0/+/+2 and PuO20/+/+2 journal January 2008
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
The generalized active space concept for the relativistic treatment of electron correlation. II. Large-scale configuration interaction implementation based on relativistic 2- and 4-spinors and its application journal August 2003
Exact decoupling of the Dirac Hamiltonian. II. The generalized Douglas–Kroll–Hess transformation up to arbitrary order journal January 2004
Systematically convergent basis sets for transition metals. I. All-electron correlation consistent basis sets for the 3d elements Sc–Zn journal August 2005
The generalized active space concept for the relativistic treatment of electron correlation. III. Large-scale configuration interaction and multiconfiguration self-consistent-field four-component methods with application to UO2 journal March 2006
An infinite-order two-component relativistic Hamiltonian by a simple one-step transformation journal February 2007
Energy-consistent relativistic pseudopotentials and correlation consistent basis sets for the 4d elements Y–Pd journal March 2007
Large-scale parallel configuration interaction. I. Nonrelativistic and scalar-relativistic general active space implementation with application to (Rb–Ba)+ journal January 2008
A survey of factors contributing to accurate theoretical predictions of atomization energies and molecular structures journal November 2008
Energy-consistent pseudopotentials and correlation consistent basis sets for the 5d elements Hf–Pt journal April 2009
Exact two-component Hamiltonians revisited journal July 2009
The Thermodynamic Properties of the f-Elements and Their Compounds. I. The Lanthanide and Actinide Metals journal December 2010
A new internally contracted multi-reference configuration interaction method journal August 2011
On the effectiveness of CCSD(T) complete basis set extrapolations for atomization energies journal July 2011
General contraction of Gaussian basis sets. I. Atomic natural orbitals for first‐ and second‐row atoms journal April 1987
An efficient internally contracted multiconfiguration–reference configuration interaction method journal November 1988
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen journal January 1989
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
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Coupled cluster theory for high spin, open shell reference wave functions journal October 1993
An exact separation of the spin‐free and spin‐dependent terms of the Dirac–Coulomb–Breit Hamiltonian journal February 1994
Formulation and implementation of a relativistic unrestricted coupled‐cluster method including noniterative connected triples journal November 1996
Transition energies of lanthanum, actinium, and eka-actinium (element 121) journal September 1998
The Thermodynamic Properties of the f -Elements and their Compounds. Part 2. The Lanthanide and Actinide Oxides journal March 2014
Composite thermochemistry of gas phase U(VI)-containing molecules journal December 2014
Correlation consistent basis sets for actinides. I. The Th and U atoms journal February 2015
Multireference configuration interaction calculations of the first six ionization potentials of the uranium atom journal November 2015
Bond energies of ThO + and ThC + : A guided ion beam and quantum chemical investigation of the reactions of thorium cation with O 2 and CO journal May 2016
Correlation consistent basis sets for lanthanides: The atoms La–Lu journal August 2016
All-electron Gaussian basis sets of double zeta quality for the actinides journal December 2016
The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors journal January 2002
Theoretical prediction of the second to fourth actinide ionization potentials journal April 2003
The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors journal October 1970
Search for effective local model potentials for simulation of quantum electrodynamic effects in relativistic calculations journal March 2003
Revision of the Douglas-Kroll transformation journal June 1989
PSEUDOPOTENTIAL STUDIES ON THE ELECTRONIC STRUCTURE OF LANTHANUM MONOHALIDES LaF , LaCl , LaBr , AND LaI journal January 2005
Comment on: "Estimating the Hartree-Fock limit from finite basis set calculations" [Jensen F (2005) Theor Chem Acc 113:267] text January 2005

Cited By (4)

Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium journal November 2017
Gas Phase Hydrolysis and Oxo‐Exchange of Actinide Dioxide Cations: Elucidating Intrinsic Chemistry from Protactinium to Einsteinium journal January 2019
Actinyl cation–cation interactions in the gas phase: an accurate thermochemical study journal January 2019
Bond energy of ThN + : A guided ion beam and quantum chemical investigation of the reactions of thorium cation with N 2 and NO journal July 2019

Similar Records

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
Chemistry
Physics