DOI: 10.1063/1.456153
OpenAccess: Closed
This work is not Open Acccess. We may still have a PDF on file in the green box below.
Share this:
Get up to 30% off our standard price for selected sequencing services covering sample extraction, library preparation, sequencing, and bioinformatic analysis.
Find out more

Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen

Thorn H. Dunning

Atomic physics
In the past, basis sets for use in correlated molecular calculations have largely been taken from single configuration calculations. Recently, Almlof, Taylor, and co‐workers have found that basis sets of natural orbitals derived from correlated atomic calculations (ANOs) provide an excellent description of molecular correlation effects. We report here a careful study of correlation effects in the oxygen atom, establishing that compact sets of primitive Gaussian functions effectively and efficiently describe correlation effects i f the exponents of the functions are optimized in atomic correlated calculations, although the primitive (s p) functions for describing correlation effects can be taken from atomic Hartree–Fock calculations i f the appropriate primitive set is used. Test calculations on oxygen‐containing molecules indicate that these primitive basis sets describe molecular correlation effects as well as the ANO sets of Almlof and Taylor. Guided by the calculations on oxygen, basis sets for use in correlated atomic and molecular calculations were developed for all of the first row atoms from boron through neon and for hydrogen. As in the oxygen atom calculations, it was found that the incremental energy lowerings due to the addition of correlating functions fall into distinct groups. This leads to the concept of c o r r e l a t i o n c o n s i s t e n t b a s i s s e t s, i.e., sets which include all functions in a given group as well as all functions in any higher groups. Correlation consistent sets are given for all of the atoms considered. The most accurate sets determined in this way, [5s4p3d2f1g], consistently yield 99% of the correlation energy obtained with the corresponding ANO sets, even though the latter contains 50% more primitive functions and twice as many primitive polarization functions. It is estimated that this set yields 94%–97% of the total (HF+1+2) correlation energy for the atoms neon through boron.

Referenced Papers:
DOI: 10.1063/1.1671837
Cited 55 times
First‐Order Wavefunctions, Orbital Correlation Energies, and Electron Affinities of First‐Row Atoms
DOI: 10.1063/1.438955
Cited 12,450 times
Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions
DOI: 10.1021/cr00074a002
Cited 691 times
Basis set selection for molecular calculations
DOI: 10.1063/1.432901
Cited 67 times
The low‐lying states of hydrogen fluoride: Potential energy curves for the x 1Σ+, 3Σ+, 3Π, and 1Π states
DOI: 10.1016/0301-0104(82)87006-7
Cited 143 times
Are atoms intrinsic to molecular electronic wavefunctions? III. Analysis of FORS configurations
DOI: 10.1063/1.452534
Cited 88 times
Full CI benchmark calculations on N2, NO, and O2: A comparison of methods for describing multiple bonds
DOI: 10.1063/1.449159
Cited 38 times
The effect of 3d shell back bonding on the binding of chlorine containing molecules
DOI: 10.1063/1.432062
Cited 59 times
Generalized valence bond calculations on the ground state (X 1Σ+g) of nitrogen
DOI: 10.1063/1.1726959
Cited 169 times
Many‐Electron Theory of Nonclosed‐Shell Atoms and Molecules. I. Orbital Wavefunction and Perturbation Theory
DOI: 10.1063/1.1726972
Cited 409 times
Electronic Structure of Diatomic Molecules. III. A. Hartree—Fock Wavefunctions and Energy Quantities for N<sub>2</sub>(<i>X</i><sup>1</sup>Σ<sub><i>g</i></sub><sup>+</sup>) and N<sub>2</sub><sup>+</sup>(<i>X</i><sup>2</sup>Σ<sub><i>g</i></sub><sup>+</sup>,<i>A</i><sup>2</sup>Π<sub><i>u</i></sub>,<i>B</i><sup>2</sup>Σ<sub><i>u</i></sub><sup>+</sup>) Molecular Ions
DOI: 10.1063/1.451917
Cited 1,017 times
General contraction of Gaussian basis sets. I. Atomic natural orbitals for first‐ and second‐row atoms
DOI: 10.1063/1.1679007
Cited 463 times
General contraction of Gaussian atomic orbitals: Core, valence, polarization, and diffuse basis sets; Molecular integral evaluation
DOI: 10.1063/1.431248
Cited 44 times
The generalized valence bond description of O2
DOI: 10.1063/1.432180
Cited 128 times
Polarization CI wavefunctions: the valence states of the NH radical
DOI: 10.1139/p73-057
Cited 131 times
The Electronic Spectrum of HF. I. The <i>B</i><sup>1</sup>Σ<sup>+</sup>–<i>X</i><sup>1</sup>Σ<sup>+</sup> Band System
DOI: 10.1063/1.1712386
Cited 150 times
Computed Ground‐State Properties of FH and CH
DOI: 10.1063/1.1696804
Cited 19 times
Electron Affinity of Oxygen
DOI: 10.1063/1.436018
Cited 626 times
An accurate three‐dimensional potential energy surface for H3
DOI: 10.1063/1.446441
Cited 103 times
Classical barrier height for H+H2→H2+H
DOI: 10.1103/physreva.9.26
Cited 108 times
Configuration-interaction study of atoms. II. Electron affinities of B, C, N, O, and F
DOI: 10.1063/1.448464
Cited 113 times
The impact of higher polarization basis functions on molecular ab initio results. I. The ground state of F2
DOI: 10.1103/physrev.131.1177
Cited 97 times
Accurate Analytical Self-Consistent Field Functions for Atoms. III. The1s22sm2pnStates of Nitrogen and Oxygen and Their Ions
DOI: 10.1063/1.1697142
Cited 1,189 times
Potential‐Energy Curves for the<i>X</i><sup>1</sup>Σ<sub><i>g</i></sub><sup>+</sup>,<i>b</i><sup>3</sup>Σ<sub><i>u</i></sub><sup>+</sup>, and<i>C</i><sup>1</sup>Π<sub><i>u</i></sub>States of the Hydrogen Molecule
Related Papers: