Scalar relativistic computations of nuclear magnetic shielding and g-shifts with the zeroth-order regular approximation and range-separated hybrid density functionals
Density functional theory (DFT) calculations of NMR chemical shifts and molecular g-tensors with Gaussian-type orbitals are implemented via second-order energy derivatives within the scalar relativistic zeroth order regular approximation (ZORA) framework. Nonhybrid functionals, standard (global) hybrids, and range-separated (Coulomb-attenuated, long-range corrected) hybrid functionals are tested. Origin invariance of the results is ensured by use of gauge-including atomic orbital (GIAO) basis functions. The new implementation in the NWChem quantum chemistry package is verified by calculations of nuclear shielding constants for the heavy atoms in HX (X=F, Cl, Br, I, At) and H2X (X = O, S, Se, Te, Po), and Te chemical shifts in a number of tellurium compounds. The basis set and functional dependence of g-shifts is investigated for 14 radicals with light and heavy atoms. The problem of accurately predicting F NMR shielding in UF6-nCln, n = 1 to 6, is revisited. The results are sensitive to approximations in the density functionals, indicating a delicate balance of DFT self-interaction vs. correlation. For the uranium halides, the results with the range-separated functionals are mixed.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 1029035
- Report Number(s):
- PNNL-SA-80687; 26690; KP1704020; TRN: US201122%%666
- Journal Information:
- Journal of Chemical Theory and Computation, Vol. 7, Issue 10
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
APPROXIMATIONS
ATOMS
CHEMICAL SHIFT
CHEMISTRY
FUNCTIONALS
HALIDES
IMPLEMENTATION
MAGNETIC SHIELDING
ORIGIN
RADICALS
SCALARS
SHIELDING
TELLURIUM COMPOUNDS
URANIUM
computations
density functional theory
zeroth order regular approximation
quantum chemistry
electron-spin-resonance
transition-metal-complexes
NMR chemical-shifts
including atomic orbitals
ab-initio calculations
g-tensors
coupling-constants
perturbation-theory
hartree-fock
excited-states
Environmental Molecular Sciences Laboratory