Polarization of core orbitals and computation of nuclear quadrupole coupling constants using Gaussian basis sets

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Abstract

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%.

Original languageEnglish (US)
Article number5648
Pages (from-to)24-31
Number of pages8
JournalJournal of Magnetic Resonance
Volume257
DOIs
StatePublished - Jun 1 2015

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quadrupoles
Polarization
orbitals
polarization
Atoms
atoms
Electric fields
exponents
gradients
radii
electric fields
augmentation

Keywords

  • Ab initio calculations
  • Electric field gradient
  • NMR
  • Nuclear quadrupole coupling
  • Rotational spectroscopy

ASJC Scopus subject areas

  • Biophysics
  • Biochemistry
  • Nuclear and High Energy Physics
  • Condensed Matter Physics

Cite this

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title = "Polarization of core orbitals and computation of nuclear quadrupole coupling constants using Gaussian basis sets",
abstract = "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{\%}.",
keywords = "Ab initio calculations, Electric field gradient, NMR, Nuclear quadrupole coupling, Rotational spectroscopy",
author = "Gerard Harbison",
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AU - Harbison, Gerard

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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

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KW - NMR

KW - Nuclear quadrupole coupling

KW - Rotational spectroscopy

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