Molecular orbital theory of the properties of inorganic and organometallic compounds. 1. STO-NG basis sets for third-row main-group elements

Pietro, William J.; Blurock, Edward S.; Hout, Robert F.; Hehre, Warren J.; Defrees, D. J.; Stewart, Robert F.

doi:10.1021/ic50210a005

Cited by 117 publications

(28 citation statements)

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“…The performance of the new 6-31G * basis set for gas phase geometry optimization is compared with a smaller STO-3G 11 and a comparable-size VDZ + polarization 12 sets for the molecules containing K and Ca in Table XI. Both of these sets do not contain valence d-type functions for K and Ca.…”

Section: Performancementioning

confidence: 99%

“…This leads to poor optimized geometries, especially for calcium containing molecules. The 6-31G and 6-31G * basis sets performs slightly worse than the old basis set by Blaudeau et al 2 We compare 6-31G * set for the molecules containing Ga through Kr with the old 6-31G * , 3 STO-3G, 11 pVDZ, 12 and cc-pVDZ 13 basis sets for gas phase geometries optimizations in Table XII. With the exception of a small STO-3G set, all basis sets have similar performance in geometry optimization, as shown by overall RRMS.…”

Section: Performancementioning

confidence: 99%

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6‐31G* basis set for third‐row atoms

et al. 2001

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Medium basis sets based upon contractions of Gaussian primitivesare developed for the third-row elements Ga through Kr. The basis functions generalize the 6-31G and 6-31G * sets commonly used for atoms up to Ar. A reexamination of the 6-31G * basis set for K and Ca developed earlier leads to the inclusion of 3d orbitals into the valence space for these atoms. Now the 6-31G basis for the whole third-row K through Kr has six primitive Gaussians for 1s, 2s, 2p, 3s, and 3p orbitals, and a split-valence pair of three and one primitives for valence orbitals, which are 4s, 4p, and 3d. The nature of the polarization functions for third-row atoms is reexamined as well. The polarization functions for K, Ca, and Ga through Kr are single set of Cartesian d-type primitives. The polarization functions for transition metals are defined to be a single 7f set of uncontracted primitives. Comparison with experimental data shows good agreement with bond lengths and angles for representative vapor-phase metal complexes.

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Section: Performancementioning

confidence: 99%

Section: Performancementioning

confidence: 99%

6‐31G* basis set for third‐row atoms

et al. 2001

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“…N, denotes the number of exchange integrals in lo6 units; Et and E, are as in Table I. The basis sets adopted are an sro-663 minimal basis set [20] and a split-valence 6-21 one [24], the latter with different values for the exponent coefficient a of the outer Gaussian, as indicated. Numbers in italics correspond to pseudoconvergent (but catastrophic) solutions.…”

Section: The Influence Of Truncation Conditions On the Calculated Wavmentioning

confidence: 99%

Near‐Hartree–Fock wave functions for solids: The case of crystalline silicon

Pisani

Dovesi

Orlando

1992

Int J of Quantum Chemistry

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Silicon is taken as a test system for assessing present-day feasibility of calculations for crystalline solids of near-Hartree-Fock quality. The calculations have been performed using CRYS-TAL, an ab initio Hartree-Fock crystalline-orbital LCAO program for periodic systems. The influence of the computational parameters that control the truncation of infinite sums on the results has been investigated; it is shown that a reasonable accuracy (numerical errors on total energy per atom below a.u.) can be obtained while keeping the computational burden within manageable limits. The effect on the results of basis-set size and quality is discussed. A number of basis sets have been tested, from minimal to relatively extended sets (28 atomic orbitals per atom). The quality of the wave function has been checked using variational criteria and also through a comparison with experimental data, such as equilibrium geometry, bulk modulus, electron charge density, and electron momentum distribution. For the latter quantities, which are a measure of the accuracy of the one-electron density matrix, the best basis sets provide agreement with experiment that is almost within the experimental error. The correlation energy has been estimated using nonlocal density functionals, based on the one-electron density matrix: After this correction, the atomization energy agrees with experiment to within 2%. The generalization of the above analysis to other crystals is briefly discussed.

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“…Better agreement was obtained for the constrained 3s = 3p 3 and for 3s = 3p = 3d fits. 4 The 4s, 4p, and constrained 4s = 4p orbitals were also optimized. The residual for the constrained case appears to be lower than what Pietro et al 4 would have obtained, although these residuals were only published in the Gaussian source code.…”

Section: ■ Resultsmentioning

confidence: 99%

“…4 The 4s, 4p, and constrained 4s = 4p orbitals were also optimized. The residual for the constrained case appears to be lower than what Pietro et al 4 would have obtained, although these residuals were only published in the Gaussian source code. 31 Our reason for this claim is that use of the published values for the exponents and contraction coefficients instead of our own optimized values resulted in a larger residual.…”

Section: ■ Resultsmentioning

confidence: 99%

On the Least-Squares Fitting of Slater-Type Orbitals with Gaussians: Reproduction of the STO-NG Fits Using Microsoft Excel and Maple

Pye

Mercer

2012

J. Chem. Educ.

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The symbolic algebra program Maple and the spreadsheet Microsoft Excel were used in an attempt to reproduce the Gaussian fits to a Slater-type orbital, required to construct the popular STO-NG basis sets. The successes and pitfalls encountered in such an approach are chronicled. C omputational chemistry, in particular, those based on ab initio quantum chemistry, has become a standard tool for many research groups and enjoys increasing use in the undergraduate curriculum. 1 One of the choices that must be made when employing these techniques is that of basis set, which is a set of functions, centered on the nuclei, which when taken as a linear combination comprise the molecular orbitals. It is this author's experience that the majority of students employing computational chemistry do not really comprehend the nature of a basis set (other than as something specified in an input file necessary to run a calculation) nor the effort required to construct them. Standardized basis sets have become common in the practice of computational chemistry. One of the most common, the STO-NG basis set, was developed over 40 years ago for the atoms H and Li through F. 2 Soon thereafter, the basis sets were extended to He, Ne, and Na through Ar. 3 Further extension of these basis sets did not come until a decade later, when basis sets for K, Ca, and Ga through Kr; 4 Rb, Sr, and In through Xe; 5 and Sc through Zn and Y through Cd 6 were published, at which point the development of the STO-NG series of basis sets appears to have stopped. One of the purposes of this article is to delineate, in part, how the STO-NG basis sets are constructed.Although few research groups use the STO-NG basis sets nowadays in production calculations, their historical importance, simple construction and efficiency of calculation makes them valuable as tools in chemical education. The most commonly used of these is the STO-3G basis set, as illustrated by the following examples. The atomic charges and dipole moments for the isoelectronic first-row hydrides and the atomic charges of their protonated forms were calculated by Greenberg, Liebman, and co-workers in a discussion of how they relate to concepts such as acidity and proton affinity. 7 The changes of the bonding σ orbital in hydrogen fluoride as a function of bond distance are illustrated by Lipkowitz. 8 The optimized bond lengths for the interstellar molecules HC 2n+1 N, n = 1−7, have been calculated by a Spanish collaboration. 9 The use of common programs to reproduce some of the very early calculations on hydrogen molecule has been espoused by Duke and O'Leary. 10 The same authors also criticize the indiscriminate use of simple molecular orbital theory to discuss the orbital energy diagram of the first-row homonuclear diatomic molecules, especially for dinitrogen. 11 Ben-Amotz and co-workers showed that, for the set of molecules cis-and trans-dichloroethene, and for methanol and methanol-d 1 , application of the scaling factor 0.8246 for the HF/STO-3G vibrational frequencies resulted in a root-mean-...

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Molecular orbital theory of the properties of inorganic and organometallic compounds. 1. STO-NG basis sets for third-row main-group elements

Cited by 117 publications

References 0 publications

6‐31G* basis set for third‐row atoms

6‐31G* basis set for third‐row atoms

Near‐Hartree–Fock wave functions for solids: The case of crystalline silicon

On the Least-Squares Fitting of Slater-Type Orbitals with Gaussians: Reproduction of the STO-NG Fits Using Microsoft Excel and Maple

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