TY - JOUR
T1 - Polarization of core orbitals and computation of nuclear quadrupole coupling constants using Gaussian basis sets
AU - Harbison, Gerard S.
N1 - Funding Information:
This work was begun on a sabbatical at the Environmental and Molecular Sciences Laboratory in (a national scientific user facility sponsored by the U.S. Department of Energy’s Office of Biological and Environmental Research ) located at Pacific Northwest National Laboratory and operated for DOE by Battelle; that sabbatical was supported by a grant from the National Institute of Health (NIH, Federal Grant EB-2050 ).
Publisher Copyright:
© 2015 Elsevier Inc.
PY - 2015/6/1
Y1 - 2015/6/1
N2 - Abstract Most standard Gaussian basis sets for first row atoms, even large sets designed to converge on a 'complete basis set' limit, systematically overestimate the electric field gradient at nuclear sites for first row atoms, resulting in errors of up to 15% in the computation of nuclear quadrupole coupling constants. This error results from a failure to include tight d functions, which permit the core 1s orbitals to distort under the influence of the field of the nuclear quadrupole. Augmentation of standard basis sets with a single set of single-exponent d functions, matched to the reciprocal square of the nominal 1s radius, reduces these errors by up to 90%.
AB - Abstract Most standard Gaussian basis sets for first row atoms, even large sets designed to converge on a 'complete basis set' limit, systematically overestimate the electric field gradient at nuclear sites for first row atoms, resulting in errors of up to 15% in the computation of nuclear quadrupole coupling constants. This error results from a failure to include tight d functions, which permit the core 1s orbitals to distort under the influence of the field of the nuclear quadrupole. Augmentation of standard basis sets with a single set of single-exponent d functions, matched to the reciprocal square of the nominal 1s radius, reduces these errors by up to 90%.
KW - Ab initio calculations
KW - Electric field gradient
KW - NMR
KW - Nuclear quadrupole coupling
KW - Rotational spectroscopy
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U2 - 10.1016/j.jmr.2015.05.002
DO - 10.1016/j.jmr.2015.05.002
M3 - Article
C2 - 26037137
AN - SCOPUS:84930637656
SN - 1090-7807
VL - 257
SP - 24
EP - 31
JO - Journal of Magnetic Resonance
JF - Journal of Magnetic Resonance
M1 - 5648
ER -