Near Hartree-Fock quality Gaussian type orbital basis sets for the first- and third-row atoms

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  • Gaussian basis sets (Quantum mechanics)

Edition Notes

StatementHarry Partridge.
SeriesNASA technical memorandum -- 101044
ContributionsAmes Research Center.
The Physical Object
Pagination1 v.
ID Numbers
Open LibraryOL17096921M

A basis set in chemistry is a set of functions used to create the molecular orbitals, which are expanded as a linear combination of such functions with the weights or coefficients to be determined. Usually these functions are atomic orbitals, in that they are centered on ise, the functions are centered on bonds or lone pairs. Pairs of functions centered in the two lobes of a p. Journal Article: Efficient method of evaluation for Gaussian Hartree-Fock exchange operator for Gau-PBE functional.   In Gaussian program one can only use GTOs (Gaussian type orbitals) and not STOs (Slater type orbitals). See Appendix B for a comparison of these basis sets. Moreover, only few basis sets (G, DGDZVP and UGBS) are available to span a sizable range (elements up to xenon) of atoms 4 to construct the familiar IP trend in a consistent manner. And. Quantum chemistry composite methods (also referred to as thermochemical recipes) are computational chemistry methods that aim for high accuracy by combining the results of several calculations. They combine methods with a high level of theory and a small basis set with methods that employ lower levels of theory with larger basis sets. They are commonly used to calculate thermodynamic.

The choice of basis set in quantum chemical calculations can have a huge impact on the quality of the results, especially for correlated ab initio methods. This article provides an overview of the development of Gaussian basis sets for molecular calculations, with a focus on four popular families of modern atom‐centered, energy‐optimized bases: atomic natural orbital, correlation. The earliest CGTO basis sets, where constructed from N GTOs that best fit the desired STO. These are called STO-NG basis sets. Gaussian basis sets are identified by abbreviations such as N-MPG *. N is the number of Gaussian primitives used for each inner-shell orbital. The hyphen indicates a split-basis set where the valence orbitals are double. Pople Basis Sets General Notation and Gaussian Primitives Basis sets denoted by the general nomenclature N-M1G or N-M11G, where N and M are integers, are called Pople basis sets. The first, N-M1G, is a split valence double zeta basis set while the second, N-M11G is a split valence triple zeta basis set.   An extended basis set of atomic functions expressed as fixed linear combinations of Gaussian functions is presented for hydrogen and the first‐row atoms carbon to fluorine. In this set, described as 4–31 G, each inner shell is represented by a single basis function taken as a sum of four Gaussians and each valence orbital is split into inner and outer parts described by three and one.

From a results point of view, for most things, it shouldn't really matter which you use - basis sets are generally constructed and labeled in such a way that for example a TZVP basis set will give comparable results whether it's using GTOs or STOs.. The cases where they're more likely to give different results will be properties that depend heavily on non-valence regions, for example, NMR data. @article{osti_, title = {Accurate correlation consistent basis sets for molecular core-valence correlation effects: The second row atoms Al-Ar and the first row atoms B-Ne revisited}, author = {Peterson, Kirk A and Dunning, Thom H}, abstractNote = {Correlation consistent basis sets for accurately describing core-core and core-valence correlation effects in atoms and molecules have been. From the point of view of ab initio (first principles) electronic structure methods, a basis set is simply a collection of functions, whose members are typically associated with one or more of the atoms in a molecule. When people say that they are "using the G basis on ethylene" they really mean that they're performing a calculation with the appropriate carbon and hydrogen G basis.

Near Hartree-Fock quality Gaussian type orbital basis sets for the first- and third-row atoms Download PDF EPUB FB2

Energy-optimized, near Hartree-Fock (NHF) quality Gaussian type orbital (GTO) basis sets are reported for the second-row (Li to Ne) and fourth-row (K to Kr) atoms.

Gaussian basis sets (24s14p, 30s19p14d, and 33s21p14d for O (3P), Ti (5S), and Ba (1S) atoms, respectively), are designed with the strategy of the Generator Coordinate Hartree-Fock method.

consistent basis sets, n gives the number of contracted Gaussian-type functions describing the valence orbitals, and the identity of the highest angular momentum functions present in the basis for second and third row atoms (n = L max for atoms Li − Ar). The number of primitive Gaussians comprising each contracted valence orbital function also.

Hartree-Fock calculations on the choice of basis sets. This experience can be transferred directly to molecular DFT cal- culations. As pointed out earlier, there is a great need for systematic comparisons between Hartree-Fock-based re- sults and DFT results. Using the same type of basis set facili.

For 36 atoms from K to Xe, compact relativistic Gaussian-type function basis sets are developed in a segmented contraction form: (/74/7) for the third row atoms and (//74) for the.

Such an approach has been utilized by Carlsen who obtained equilibrium geometries for a number of polyatomic molecules in excellent agreement with those derived from near‐limiting Hartree‐Fock procedures simply by using the 4–31G split‐valence basis set (Ref.

5) supplemented by a single set of Gaussian s‐ and p‐type functions placed. These Dunning bases are commonly denoted, for example, as follows for first-row atoms: (10s,6p/5s,4p), which means that 10 s-type primitive GTOs have been contracted to produce 5 separate s-type CGTOs and that 6 primitive p-type GTOs were contracted to generate 4 separate p-type CGTOs.

More recent basis sets from the Dunning group are given in. H. Partridge, Near Hartree–Fock Quality Gaussian Type Orbital Basis Sets for the First- and Third-row Atoms, NASA Tech. Mem.Jan. Google Scholar   H. Partridge, Near Hartree–Fock quality gaussian type orbital basis sets for the first- and third-row atoms, NASA (Natl.

Aeron. Space Adm.) Tech. Mem.Jan. Google Scholar. Which is the best set of options for Gaussian09 that can emulate a home-made Hartree-Fock program (written following closely Szabo's book [1]).

[1] A. Szabo. The Generator Coordinate Hartree–Fock (GCHF) method is employed to generate uncontracted 15s and 18s11p gaussian basis sets for the H, C and O atoms, respectively.

Accurate Gaussian basis sets for atoms from H to Ba were obtained by means of the generator coordinate Hartree-Fock (GCHF) method based on a polynomial expansion to discretize the Griffin-Wheeler-Hartree-Fock equations (GWHF).

The discretization of the GWHF equations in this procedure is based on a mesh of points not equally distributed in contrast with the original GCHF. For the second-row atoms, Li through Ne, four minimal Gaussian basis sets are generated.

The first one consists of three-term contraction of primitive Gaussian-type orbitals for 1s, 2s, and 2p. Pre have been performed by the GAUSSIAN 92/DFT vious experience with post-Hartree-Fock methods system of programs [ 9 ]. The peculiar characteristics [ 20,21 ] suggests that the Huzinaga (9, 5) primitive of the electronic code are the use of Gaussian basis set.

The smallest basis sets are called minimal basis sets. A minimal basis set is one in which, on each atom in the molecule, a single basis function is used for each orbital in a Hartree–Fock calculation on the free atom.

For atoms such as lithium, basis functions of p type are also added to the basis functions that correspond to the 1s and 2s. H. Partridge, Near Hartree–Fock quality gaussian type orbital basis sets for the first- and third-row atoms, NASA Technical MemorandumJanuary Google Scholar [17].

The now well‐established L2 techniques applied to the description of the electronic continuum of small molecules and generally implemented with suitable oscillating basis sets are here adapted and used in connection with Gaussian type orbital (GTO) functions. As a test, a K‐matrix approach associated with extended sets of GTOs is employed to compute with satisfactory accuracy partial wave.

Last updated on: 05 January [G16 Rev. C] Quick Links. Basis Sets; Density Functional (DFT) Methods; Solvents List SCRF. Partridge, Near Hartree-Fock quality Gaussian type orbital basis sets for the first- and third-row atoms, Technical Memorandum (NASA, Ames.

The measured orbital momentum profiles are compared with a variety of Hartree–Fock treatments ranging from a minimal STO-3G basis to near Hartree–Fock limit quality basis sets including a contracted Gaussian type orbital (GTO) calculation developed in the course of the present collaborative work.

within the “functionspace”of the basis set used (so solutions within the STO-3G set of functions, or the G set, etc.) •Improving the quality of the basis set requires increasing the number of CGs •A complete basis set can represent exactly any molecular orbital •Unfortunately, complete basis sets tend to have an infinite number.

Static correlation energies (Estat) are calculated in a range of basis sets for a chemically diverse collection of atoms and molecules. The reliability of a basis set in capturing Estat is assessed according to the following: mean and maximum absolute deviations from near-exact Estat estimates, monotonic convergence to the complete basis set limit, and ability to capture Estat accurately.

Auxiliary basis sets for use in the resolution of the identity (RI) approximation in explicitly correlated methods are presented for the elements H–Ar. These extend the cc-pVnZ-F12/OptRI (n = D–Q) auxiliary basis sets of Peterson and co-workers by the addition of a small number of s- and p-functions, optimized so as to yield the greatest complementary auxiliary basis set (CABS) singles.

Rationale. The use of Gaussian orbitals in electronic structure theory (instead of the more physical Slater-type orbitals) was first proposed by Boys in The principal reason for the use of Gaussian basis functions in molecular quantum chemical calculations is the 'Gaussian Product Theorem', which guarantees that the product of two GTOs centered on two different atoms is a finite sum of.

The G3Large basis set for the third-row transition metal atoms is a contracted Gaussian set with diffuse and polariza-tion functions. The contracted set was derived similar to the G3Large basis set for third-row nontransition metal elements in G3 theory This procedure involves a full optimization of the basis set on atomic restricted open.

In quantum chemistry, a Gaussian type orbital (GTO) is an atomic orbital used in linear combinations forming molecular were proposed by Boys as early asand are at present the basis functions most generally used in quantum chemical program packages.

A GTO is a real-valued function of a 3-dimensional vector r = (x, y, z), the vector pointing from an origin to the position.

Molecular orbital theory of the properties of inorganic and organometallic compounds. -3G basis sets for first- and second-row transition metals William J. Pietro, Warren J. Hehre Journal of Computational Chemistry 4 (2), construction of efficient Gaussian basis sets, whether of the Pople,44 Dunning,45 or Jensen46 type.

In this paper, we examine the Gaussian expansions of a variety of orbitals and present a general approach for predicting and rationalizing the rate of convergence of the energies of such expansions.

We use atomic units throughout. Gaussian basis set for hydrogen through lanthanum generated with the generator coordinate Hartree-Fock method.

Chemical Physics, (–), JORGE, F.; DE CASTRO, E. Improved generator coordinate Hartree– Fock method: application to first-row atoms. Chemical Physics Letters, (–), JORGE, F.; MUNIZ, E. The new sets, denoted cc-pVnZ-F12 (n = D,T,Q), are similar in size and construction to the std.

aug-cc-pVnZ and aug-cc-pV(n + d)Z basis sets, but the new sets are shown in the present work to yield much improved convergence toward the complete basis set limit in MP2-F12/3C calcns.

on several small mols. involving elements of both the first and. A minimum basis set is one in which, on each atom in the molecule, a single basis function is used for each orbital in a Hartree-Fock calculation on the free atom.

However, for atoms such as lithium, basis functions of p type are added to the basis functions corresponding to the .A contracted Gaussian basis set (6‐G**) is developed by optimizing exponents and coefficients at the Mo/ller–Plesset (MP) second‐order level for the ground states of first‐row atoms.

This has a triple split in the valence s and p shells together with a single set of. F. Weigend, F. Furche, and R. Ahlrichs, “Gaussian basis sets of quadruple zeta valence quality for atoms H-Kr,” J. Chem. Phys., () Weigend05 F. Weigend and R. Ahlrichs, “Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy,” Phys.