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Two-Component Relativistic Calculations of Electric-Field Gradients Using Exact Decoupling Methods: Spin–orbit and Picture-Change Effects

Journal Article · · Journal of Chemical Theory and Computation
DOI:https://doi.org/10.1021/ct300623j· OSTI ID:2479696
 [1];  [2];  [2]
  1. University at Buffalo, State University of New York, NY (United States)
  2. ETH Zürich (Switzerland)
+ Show Author Affiliations
Electric field gradients (EFGs) for heavy nuclei in diatomic molecules (hydrogen halides and group-13 iodides), uranyl (UO22+), and a uranyl carbonate complex, were computed with different formally exactly (or nearly exactly) decoupled two-component relativistic Hamiltonians: the “exact two-component” (X2C) method, the Barysz–Sadlej–Snijders (BSS) approach, and up to 35th order in the Douglas–Kroll–Hess (DKH) expansion, utilizing a new implementation in the open-source NWChem quantum chemistry package. Results from two-component Hartree–Fock and density functional theory (DFT) calculations at the scalar relativistic approximation as well as including spin–orbit coupling are reported. Picture-change corrected EFGs obtained with X2C, BSS, and high-order DKH are shown to be numerically equivalent. Effects from spin–orbit coupling on the EFGs tend to be moderate but should not be excluded for reliable predictions. Picture-change effects on the EFG of a heavy atom can be as large as the correct picture-change corrected value, as is shown for the uranium EFG in the uranyl systems. The results demonstrate the necessity of simultaneously including spin–orbit and picture-change effects in calculations of heavy atom EFGs.
Research Organization:
University at Buffalo, State University of New York, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
SC0001136
OSTI ID:
2479696
Journal Information:
Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 11 Vol. 8; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (84)

The role of databases in support of computational chemistry calculations journal October 1996
Nonsingular two/one-component relativistic Hamiltonians accurate through arbitrary high order in ?2 journal January 1997
Picture change and calculations of expectation values in approximate relativistic theories journal January 1998
Accurate electric field gradients for the coinage metal chlorides using the PCNQM method journal January 2000
Analysis of electric field gradient tensors at quadrupolar nuclei in common structural motifs journal March 2010
Relativistic Hamiltonians for Chemistry: A Primer journal November 2011
A systematic sequence of relativistic approximations journal April 2002
Solid-state NMR spectroscopy of the quadrupolar halogens: chlorine-35/37, bromine-79/81, and iodine-127 journal January 2006
Basis set expansion of the dirac operator without variational collapse journal January 1984
On convergence of the normalized elimination of the small component (NESC) method journal August 2006
Exact decoupling of the relativistic Fock operator journal January 2012
Relativistic effects in nuclear quadrupole coupling journal July 1997
Relativistic electron densities in the four-component Dirac representation and in the two-component picture journal May 2000
Relativistically parameterized extended hückel calculations. IX. An iterative version with applications to some xenon, thorium and uranium compounds journal February 1986
Relativistic calculations of electric field gradients using the Douglas–Kroll method journal July 2002
High performance computational chemistry: An overview of NWChem a distributed parallel application journal June 2000
Two-component methods of relativistic quantum chemistry: from the Douglas–Kroll approximation to the exact two-component formalism journal October 2001
On the bonding and the electric field gradient of the uranyl ion journal January 1998
Relativistic one-electron Hamiltonians `for electrons only' and the variational treatment of the Dirac equation journal December 1997
NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations journal September 2010
A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP) journal July 2004
Non-iterative approach to the infinite-order two-component (IOTC) relativistic theory and the non-symmetric algebraic Riccati equation journal September 2007
Theoretical Actinide Molecular Science journal January 2010
Basis Set Exchange:  A Community Database for Computational Sciences journal March 2007
The electronic structure of actinide-containing molecules: a challenge to applied quantum chemistry journal July 1991
Actinide Carbonte Complexes and Their Importance in Actinide Environmental Chemistry journal January 1995
Electric Field Gradients Calculated from Two-Component Hybrid Density Functional Theory Including Spin−Orbit Coupling journal August 2010
Gaussian Basis Set and Planewave Relativistic Spin−Orbit Methods in NWChem journal January 2009
An 17O NMR and Quantum Chemical Study of Monoclinic and Orthorhombic Polymorphs of Triphenylphosphine Oxide journal July 2003
Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields journal November 1994
Experimental and Theoretical 17 O NMR Study of the Influence of Hydrogen-Bonding on CO and O−H Oxygens in Carboxylic Solids journal January 2006
New Relativistic ANO Basis Sets for Transition Metal Atoms journal July 2005
Nuclear Quadrupole Moment of 119Sn journal January 2008
Does a Molecule-Specific Density Functional Give an Accurate Electron Density? The Challenging Case of the CuCl Electric Field Gradient journal February 2012
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy journal January 2005
Nuclear quadrupole moments for Al27 and Ga69 derived from four-component molecular coupled cluster calculations journal June 2001
Accurate relativistic Gaussian basis sets for H through Lr determined by atomic self-consistent field calculations with the third-order Douglas–Kroll approximation journal September 2001
Comparison of ab initio and density functional calculations of electric field gradients: The Fe57 nuclear quadrupole moment from Mössbauer data journal October 2001
Interfacing relativistic and nonrelativistic methods. IV. One- and two-electron scalar approximations journal November 2001
Infinite-order two-component theory for relativistic quantum chemistry journal February 2002
The accuracy of density functionals for electric field gradients. Test calculations for ScX, CuX and GaX (X=F, Cl, Br, I, H and Li) journal September 2003
Representation of the exact relativistic electronic Hamiltonian within the regular approximation journal December 2003
Exact decoupling of the Dirac Hamiltonian. I. General theory journal August 2004
Exact decoupling of the Dirac Hamiltonian. II. The generalized Douglas–Kroll–Hess transformation up to arbitrary order journal January 2004
Connection between the regular approximation and the normalized elimination of the small component in relativistic quantum theory journal February 2005
Calculation of electric-field gradients based on higher-order generalized Douglas–Kroll transformations journal May 2005
Accurate and efficient treatment of two-electron contributions in quasirelativistic high-order Douglas-Kroll density-functional calculations journal November 2005
Quasirelativistic theory equivalent to fully relativistic theory journal December 2005
Exact decoupling of the Dirac Hamiltonian. III. Molecular properties journal February 2006
Exact decoupling of the Dirac Hamiltonian. IV. Automated evaluation of molecular properties within the Douglas-Kroll-Hess theory up to arbitrary order journal February 2006
Infinite-order quasirelativistic density functional method based on the exact matrix quasirelativistic theory journal July 2006
Comment on “Quasirelativistic theory equivalent to fully relativistic theory” [J. Chem. Phys. 123, 241102 (2005)] journal September 2006
An infinite-order two-component relativistic Hamiltonian by a simple one-step transformation journal February 2007
Quasirelativistic theory. II. Theory at matrix level journal March 2007
Analytic high-order Douglas-Kroll-Hess electric field gradients journal August 2007
Making four- and two-component relativistic density functional methods fully equivalent based on the idea of “from atoms to molecule” journal September 2007
An arbitrary order Douglas–Kroll method with polynomial cost journal January 2009
Exact two-component Hamiltonians revisited journal July 2009
The molecular mean-field approach for correlated relativistic calculations journal September 2009
Probing the oxygen environment in UO22+ by solid-state O17 nuclear magnetic resonance spectroscopy and relativistic density functional calculations journal February 2010
Perspective: Relativistic effects journal April 2012
A new mixing of Hartree–Fock and local density‐functional theories journal January 1993
An exact separation of the spin‐free and spin‐dependent terms of the Dirac–Coulomb–Breit Hamiltonian journal February 1994
Local unitary transformation method for large-scale two-component relativistic calculations: Case for a one-electron Dirac Hamiltonian journal June 2012
Local relativistic exact decoupling journal June 2012
Interfacing relativistic and nonrelativistic methods. I. Normalized elimination of the small component in the modified Dirac equation journal June 1997
Interfacing relativistic and nonrelativistic methods. II. Investigation of a low-order approximation journal September 1998
Molecular relativistic calculations of the electric field gradients at the nuclei in the hydrogen halides journal December 1998
The accuracy of current density functionals for the calculation of electric field gradients: A comparison with ab initio methods for HCl and CuCl journal August 1999
Interfacing relativistic and nonrelativistic methods. III. Atomic 4-spinor expansions and integral approximations journal December 1999
Density functional calculations of nuclear quadrupole coupling constants in the zero-order regular approximation for relativistic effects journal May 2000
Molecular relativistic electric field gradient calculations suggest revision of the value of the nuclear electric quadrupole moment of 127I journal July 2003
The uranyl ion revisited: the electric field gradient at U as a probe of environmental effects journal March 2005
Quasirelativistic theory I. Theory in terms of a quasi-relativistic operator journal July 2006
Year-2008 nuclear quadrupole moments journal August 2008
Ideas of relativistic quantum chemistry journal July 2010
Matrix representation of operator products journal February 1984
Relativistic atomic orbital contractions and expansions: magnitudes and explanations journal October 1990
Introduction to Relativistic Quantum Chemistry January 2007
Density-functional exchange-energy approximation with correct asymptotic behavior journal September 1988
Cu63andAu197nuclear quadrupole moments from four-component relativistic density-functional calculations using correct long-range exchange journal September 2007
Density-functional approximation for the correlation energy of the inhomogeneous electron gas journal June 1986
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density journal January 1988
Mössbauer studies of electric hyperfine interactions in U 234 , U 236 , U 238 journal April 1974

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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