Polarization functions for gaussian basis sets for the first row atoms (original) (raw)
Related papers
Effect of the basis set on the computation of molecular polarization
The Journal of Physical Chemistry, 1993
The effect of the basis set on the polarization contribution to the interaction energy was studied by means of the polarization energy maps for hydrogen cyanide, formaldehyde, and urea. The study was carried out at the SCFlevel. Basis sets included in the present study were the split-valence 3-21G, 6-31G, 6-31G*, and 6-31G** basis sets and Dunning's 9s5p contracted to a double zeta (DZ), the DZ plus one set of polarization functions (DZP), or two (DZPP'). A DZ plus one set of polarization functions with exponents optimized to yield reliable polarizabilities (DZP') was also used. The polarization a t each point was calculated as the difference between the interaction energy of the molecule with a positive point charge and the molecular electrostatic potential at this point. Maps were computed for three different planes at 2, 4, and 8 bohrs from the plane containing the heavy atoms of the molecule. Comparison of the results shows a correlation between the percentage of the polarization achieved with the ability of a basis set to provide reasonable estimates of dipole polarizabilities. Thus, a basis set with polarization functions optimized to obtain reliable polarizabilities was necessary to achieve good quantitative descriptions of molecular polarization potentials.
Journal of Computational Methods in Sciences and Engineering, 2004
The rational design rules for atomic Gaussian basis sets, tailored for the calculations of molecular polarizabilities αij and hyperpolarizabilities β ijk at the SCF level, are elaborated. The sequence of the optimized polarization sets (2d), (3d), (4d), (3d1f), (4d3f) for the first-row atoms from B to F is constructed, the optimization technique is supposed to provide a rapid convergence of both αij and β ijk with the size of the polarization set. Adding of these polarization sets to the [6s4p] and [6s5p] substrates, derived from the energy-optimized (10s6p) primitive set of Huzinaga, gives the [6s4pNdMf] and [6s5pNdMf] bases families. They are combined with the corresponding [4sNpMd] and [5sNpMd] bases for Hydrogen built up in the same manner. The convergence of SCF results with the size of the basis set has been thoroughly investigated by the examples of H2CO, CH3CN, and HCN molecules. It has been established that both αij and β ijk values converge to their saturation limits at the [6s4p3d/4s3p] level. This basis set provides the results, which are very close to near HF limit values, estimated with the most sophisticated polarized Gaussian basis sets used up to now.
Theoretical Chemistry Accounts, 2005
Following the recent studies of basis sets explicitly dependent on oscillatory external electric field we have investigated the possibility of some further truncation of the so-called polarized basis sets without any major deterioration of the computed data for molecular dipole moments, dipole polarizabilities, and related electric properties of molecules. It has been found that basis sets of contracted Gaussian functions of the form [3s1p] for H and [4s3p1d] for the first-row atoms can satisfy this requirement with particular choice of contractions in their polarization part. With m denoting the number of primitive GTOs in the contracted polarization function, the basis sets devised in this article will be referred to as the ZmPol sets. In comparison with earlier, medium-size polarized basis sets (PolX), these new ZmPol basis sets are reduced by 2/3 in their size and lead to the order of magnitude computing time savings for large molecules. Simultaneously, the dipole moment and polarizability data remain at almost the same level of accuracy as in the case of the PolX sets. Among a variety of possible applications in computational chemistry, the ZmPolX are also to be used for calculations of frequencies and intensities in the Raman spectra of large organic molecules (see Part II, this issue).
On polarization functions for Gaussian basis sets
Journal of Molecular Modeling, 2020
In this work, we introduce a technique to choose polarization functions directly from the primitive set of Gaussian exponent without the necessity to optimize or even reoptimized them. For this purpose, initially, we employed Gaussian basis sets generated by using the Polynomial Generator Coordinate Hartree-Fock (PGCHF) method, and later we extended our technique to the cc-pVQZ and pc-3 Gaussian basis sets in order to show how our technique works and how good it is. Using the new polarized basis sets, from our technique, total electronic energies, equilibrium geometries, and vibrational frequencies were calculated for a set of molecules containing atoms from H(Z = 1) to Ba(Z = 56). The technique presented here can be used with any Gaussian basis set flexible (large) enough and also can be used to choose Gaussian basis set exponents from one basis set to another as polarization functions.
On the Use of an Interpolation Approach for the Choice of Gaussian Polarization Functions
Journal of the Brazilian Chemical Society
In this work, we tested a linear interpolation approach in order to select polarization functions (exponents) to be used with Gaussian basis sets. The Gaussian primitive functions were generated here for Ga to Kr and also for Sc to Cu. The general contraction method was used for the construction of contracted Gaussian basis sets of 6Z and 7Z quality. Polarization functions were added to the contracted bases by explicit optimization and also by interpolation of exponents. The performance of the contracted basis sets, augmented with polarization functions obtained by interpolation, was tested with molecular configurations interaction single and double excitations (CISD) and density functional theory (DFT) calculations for the systems Se, Se 2 , Se 6 , Ge 2 , CrH and FeH. The outcomes obtained in this work with interpolated polarization functions agreed very well with the ones augmented with polarization functions obtained by explicit optimization. The interpolation methodology presented here is useful to generate polarization functions for any Gaussian basis set in different series of atoms of the periodic table.
Polarization consistent basis sets: Principles
The Journal of Chemical Physics, 2001
The basis set convergence of Hartree-Fock energies for the H 2 , H 3 ϩ , C 2 , N 2 , N 4 , O 2 , O 3 , F 2 , HF, and CH 4 molecules is analyzed using optimized basis functions. Based on these analysis a sequence of polarization consistent basis sets are proposed which should be suitable for systematically improving Hartree-Fock and density functional energies. Analogous to the correlation consistent basis sets designed for correlation energies, higher angular momentum functions are included based on their energetical importance. In contrast to the correlation consistent basis sets, however, the importance of higher angular momentum functions decreases approximately geometric, rather than arithmetic. It is shown that it is possible to design a systematic sequence of basis sets for which results converge monotonic to the Hartree-Fock limit. The primitive basis sets can be contracted by a general contraction scheme. It is found that polarization consistent basis sets provide a faster convergence than the correlation consistent basis sets. Results obtained with polarization consistent basis sets can be further improved by extrapolation.
Contracted Gaussian bases for the first-row atoms applied to neutral and charged diatomic molecules
Journal of Molecular Structure THEOCHEM
A set of contracted Gaussian bases generated with the Generator Coordinate Hartree–Fock method for first-row atoms (H, Li–Ne) is applied to perform molecular ab initio calculations. The primitives 18s 12p Gaussian basis sets were contracted to (5s) for H atom and (7s 5p) for Li–Ne atoms by a standard procedure and enriched with polarization functions in order to perform the calculations. The contracted Gaussian basis sets are then tested for H2, BH, B2, C2, N2, O2, F2, HF, LiF, BeO, BF, CN−, CO and NO+ molecular species. The molecular properties of interest are Koopmans' ionization potential, bond distances and vibrational frequencies at MP2 level and dipole moments at HF and MP2 levels. The results obtained show that the contracted Gaussian bases used in this work is a useful alternative for ab initio molecular calculations, and that the Generator Coordinate Hartree–Fock method is a legitimate alternative for selection of contracted and polarized Gaussian basis sets.
On Hartree–Fock Dipole Polarizabilities of Molecules, Ions, and Defects in Dunning's Basis Sets
Journal of Structural Chemistry - J STRUCT CHEM-ENGL TR, 2001
Standard Pople type basis sets generally used to solve applied problems are not quite suitable for ab initio calculations of molecular polarizabilities. Even extended basis sets including diffuse AO such as 6-311++G(d, p) lead to understated dipole polarizabilities α. Previously, better AO basis sets were proposed for polarizability calculations. Among these, Sadley's basis [1, proved to be the best one, as demonstrated by α calculations for benzene [3] and a number of DNA nitrous bases . Miscellaneous more complex basis sets were also discussed [5-9].
International Journal of Quantum Chemistry, 1988
This paper analyzes the use of electric-field-variant (EFV) atomic orbitals in calculations of molecular polarizabilities using the finite field approximation. It is shown that, in the absence of an external electric field, the optimal positions of the orbital centers which minimize the total energy are already shifted with respect to the atomic sites and that these optimal positions constitute a better starting point to compute molecular polarizabilities by the finite field method. The technique is applied to the hydrogen molecule and to the alkane series C, Hz,+z, n = 1 , 2 , 3 , 4 , 5 , 6 in the framework of a floating spherical gaussian orbital-EFv basis.
Static Polarizabilities at the Basis Set Limit: A Benchmark of 124 Species
Benchmarking molecular properties with Gaussian-type orbital (GTO) basis sets can be challenging, because one has to assume that the computed property is at the complete basis set (CBS) limit, without a robust measure of the error. Multiwavelet (MW) bases can be systematically improved with a controllable error, which eliminates the need for such assumptions. In this work, we have used MWs within Kohn−Sham density functional theory to compute static polarizabilities for a set of 92 closed-shell and 32 open-shell species. The results are compared to recent benchmark calculations employing the GTO-type aug-pc4 basis set. We observe discrepancies between GTO and MW results for several species, with open-shell systems showing the largest deviations. Based on linear response calculations, we show that these discrepancies originate from artifacts caused by the field strength and that several polarizabilies from a previous study were contaminated by higher order responses (hyperpolarizabilities). Based on our MW benchmark results, we can affirm that aug-pc4 is able to provide results close to the CBS limit, as long as finite difference effects can be controlled. However, we suggest that a better approach is to use MWs, which are able to yield precise finite difference polarizabilities even with small field strengths.