Basis set effects on the hyperpolarizability of CHCl3: Gaussian-type orbitals, numerical basis sets and real-space grids

Relativistic many-body perturbation theory calculations on Xe have been performed with basis sets of well-tempered Gaussian-type functions of Huzinaga and Klobukowski. The well-tempered Gaussian-type functions were used in both contracted and uncontracted form. The contracted Gaussian basis sets used in the relativistic many-body study are designed to retain flexibility for correlated calculations both in the core and the valence region. They reproduce second-order energy corrections computed with uncontracted Gaussian basis sets to an accuracy of greater than 99%. A compact representation of the relativistic wave functions in terms of contracted well-tempered Gaussian functions used in the present study provides a useful means of curtailing integral storage requirements and the time needed for correlated calculations, while still retaining high accuracy in relativistic electron correlation effects. Keywords: Dirac–Fock, relativistic many-body perturbation theory, well-tempered Gaussian basis, xenon.

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A systematic preparation of new contracted Gaussian‐type orbital basis sets. II. Test basis set for Cu2 molecule with and without splitting of the outer orbitals

The Journal of Chemical Physics ◽

10.1063/1.438863 ◽

1980 ◽

Vol 72 (1) ◽

pp. 399-405 ◽

Cited By ~ 91

Author(s):

Hiroshi Tatewaki ◽

Sigeru Huzinaga

Keyword(s):

Basis Set ◽

Basis Sets ◽

Gaussian Type ◽

Type Orbital ◽

Orbital Basis

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A Systematic DFT Study of Two Elementary Steps Involving Hydrogen Peroxide and the Hydroxyl Radical in the Fenton Reaction

10.26434/chemrxiv.6160142 ◽

2018 ◽

Author(s):

Danilo Carmona ◽

David Contreras ◽

Oscar A. Douglas-Gallardo ◽

Stefan Vogt-Geisse ◽

Pablo Jaque ◽

...

Keyword(s):

Hydrogen Peroxide ◽

Hydroxyl Radical ◽

Ab Initio ◽

Fenton Reaction ◽

Basis Set ◽

Basis Sets ◽

Dft Methods ◽

Elementary Steps ◽

Oxygen Oxygen ◽

Complete Basis Set

The Fenton reaction plays a central role in many chemical and biological processes and has various applications as e.g. water remediation. The reaction consists of the iron-catalyzed homolytic cleavage of the oxygen-oxygen bond in the hydrogen peroxide molecule and the reduction of the hydroxyl radical. Here, we study these two elementary steps with high-level ab-initio calculations at the complete basis set limit and address the performance of different DFT methods following a specific classification based on the Jacob´s ladder in combination with various Pople's basis sets. Ab-initio calculations at the complete basis set limit are in agreement to experimental reference data and identified a significant contribution of the electron correlation energy to the bond dissociation energy (BDE) of the oxygen-oxygen bond in hydrogen peroxide and the electron affinity (EA) of the hydroxyl radical. The studied DFT methods were able to reproduce the ab-initio reference values, although no functional was particularly better for both reactions. The inclusion of HF exchange in the DFT functionals lead in most cases to larger deviations, which might be related to the poor description of the two reactions by the HF method. Considering the computational cost, DFT methods provide better BDE and EA values than HF and post--HF methods with an almost MP2 or CCSD level of accuracy. However, no systematic general prediction of the error based on the employed functional could be established and no systematic improvement with increasing the size in the Pople's basis set was found, although for BDE values certain systematic basis set dependence was observed. Moreover, the quality of the hydrogen peroxide, hydroxyl radical and hydroxyl anion structures obtained from these functionals was compared to experimental reference data. In general, bond lengths were well reproduced and the error in the angles were between one and two degrees with some systematic trend with the basis sets. From our results we conclude that DFT methods present a computationally less expensive alternative to describe the two elementary steps of the Fenton reaction. However, choice of approximated functionals and basis sets must be carefully done and the provided benchmark allows a systematic validation of the electronic structure method to be employed

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DFT Benchmark Study of the O--O Bond Dissociation Energy in Peroxides Validated with High-Level Ab-Initio Calculations

10.26434/chemrxiv.8217221.v1 ◽

2019 ◽

Author(s):

Danilo Carmona ◽

Pablo Jaque ◽

Esteban Vöhringer-Martinez

Keyword(s):

Reference Value ◽

Basis Set ◽

Basis Sets ◽

Mean Deviation ◽

Bond Dissociation ◽

Dissociation Energies ◽

The Mean ◽

Experimental Values ◽

High Level ◽

Almost All

<div><div><div><p>Peroxides play a central role in many chemical and biological pro- cesses such as the Fenton reaction. The relevance of these compounds lies in the low stability of the O–O bond which upon dissociation results in radical species able to initiate various chemical or biological processes. In this work, a set of 64 DFT functional-basis set combinations has been validated in terms of their capability to describe bond dissociation energies (BDE) for the O–O bond in a database of 14 ROOH peroxides for which experimental values ofBDE are available. Moreover, the electronic contributions to the BDE were obtained for four of the peroxides and the anion H2O2− at the CBS limit at CCSD(T) level with Dunning’s basis sets up to triple–ζ quality provid- ing a reference value for the hydrogen peroxide anion as a model. Almost all the functionals considered here yielded mean absolute deviations around 5.0 kcal mol−1. The smallest values were observed for the ωB97 family and the Minnesota M11 functional with a marked basis set dependence. Despite the mean deviation, order relations among BDE experimental values of peroxides were also considered. The ωB97 family was able to reproduce the relations correctly whereas other functionals presented a marked dependence on the chemical nature of the R group. Interestingly, M11 functional did not show a very good agreement with the established order despite its good performance in the mean error. The obtained results support the use of similar validation strategies for proper prediction of BDE or other molecular properties by DF Tmethods in subsequent related studies.</p></div></div></div>

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Benchmark of Simplified Time-Dependent Density Functional Theory for UV-Vis Spectral Properties of Porphyrinoids

10.26434/chemrxiv.9912860 ◽

2019 ◽

Author(s):

Kamal Batra ◽

Stefan Zahn ◽

Thomas Heine

Keyword(s):

Density Functional Theory ◽

Density Functional ◽

Large Scale ◽

Absolute Error ◽

Time Dependent ◽

Basis Set ◽

Basis Sets ◽

Functional Theory ◽

Framework Materials ◽

Dependent Density

<p>We thoroughly benchmark time-dependent density- functional theory for the predictive calculation of UV/Vis spectra of porphyrin derivatives. With the aim to provide an approach that is computationally feasible for large-scale applications such as biological systems or molecular framework materials, albeit performing with high accuracy for the Q-bands, we compare the results given by various computational protocols, including basis sets, density-functionals (including gradient corrected local functionals, hybrids, double hybrids and range-separated functionals), and various variants of time-dependent density-functional theory, including the simplified Tamm-Dancoff approximation. An excellent choice for these calculations is the range-separated functional CAM-B3LYP in combination with the simplified Tamm-Dancoff approximation and a basis set of double-ζ quality def2-SVP (mean absolute error [MAE] of ~0.05 eV). This is not surpassed by more expensive approaches, not even by double hybrid functionals, and solely systematic excitation energy scaling slightly improves the results (MAE ~0.04 eV). </p>

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AlN Nanotubes: A DFT Study of Al-27 and N-14 Electric Field Gradient Tensors

Zeitschrift für Naturforschung A ◽

10.1515/zna-2007-1206 ◽

2007 ◽

Vol 62 (12) ◽

pp. 711-715 ◽

Cited By ~ 2

Author(s):

Ahmad Seif ◽

Mahmoud Mirzaei ◽

Mehran Aghaie ◽

Asadollah Boshra

Keyword(s):

Electric Field ◽

Electric Field Gradient ◽

Field Gradient ◽

Density Functional ◽

Quadrupole Coupling Constant ◽

Basis Set ◽

Basis Sets ◽

B3lyp Method ◽

Package Program ◽

Nqr Parameters

Density functional theory (DFT) calculations were performed to calculate the electric field gradient (EFG) tensors at the sites of aliminium (27Al) and nitrogen (14N) nuclei in an 1 nm of length (6,0) single-walled aliminium nitride nanotube (AlNNT) in three forms of the tubes, i. e. hydrogencapped, aliminium-terminated and nitrogen-terminated as representatives of zigzag AlNNTs. At first, each form was optimized at the level of the Becke3,Lee-Yang-Parr (B3LYP) method, 6-311G∗∗ basis set. After, the EFG tensors were calculated at the level of the B3LYP method, 6-311++G∗∗ and individual gauge for localized orbitals (IGLO-II and IGLO-III) types of basis sets in each of the three optimized forms and were converted to experimentally measurable nuclear quadrupole resonance (NQR) parameters, i. e. quadrupole coupling constant (qcc) and asymmetry parameter (ηQ). The evaluated NQR parameters revealed that the considered model of AlNNT can be divided into four equivalent layers with similar electrostatic properties.With the exception of Al-1, all of the three other Al layers have almost the same properties, however, N layers show significant differences in the magnitudes of the NQR parameters in the length of the nanotube. Furthermore, the evaluated NQR parameters of Al-1 in the Al-terminated form and N-1 in the N-terminated form revealed the different roles of Al (base agent) and of N (acid agent) in AlNNT. All the calculations were carried out using the GAUSSIAN 98 package program.

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The Sternheimer approach to all-electron real-space density-functional perturbation theory with atomic basis set

AIP Advances ◽

10.1063/5.0029361 ◽

2021 ◽

Vol 11 (1) ◽

pp. 015224

Author(s):

Honghui Shang

Keyword(s):

Perturbation Theory ◽

Density Functional ◽

Real Space ◽

Basis Set ◽

Space Density ◽

Density Functional Perturbation Theory

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The S66 Non-Covalent Interactions Benchmark Reconsidered Using Explicitly Correlated Methods Near the Basis Set Limit

Australian Journal of Chemistry ◽

10.1071/ch17588 ◽

2018 ◽

Vol 71 (4) ◽

pp. 238 ◽

Cited By ~ 13

Author(s):

Manoj K. Kesharwani ◽

Amir Karton ◽

Nitai Sylvetsky ◽

Jan M. L. Martin

Keyword(s):

Computational Cost ◽

The Other ◽

Basis Set ◽

Basis Sets ◽

Explicitly Correlated ◽

Non Covalent Interactions ◽

Explicitly Correlated Methods ◽

The One ◽

High Level ◽

Covalent Interactions

The S66 benchmark for non-covalent interactions has been re-evaluated using explicitly correlated methods with basis sets near the one-particle basis set limit. It is found that post-MP2 ‘high-level corrections’ are treated adequately well using a combination of CCSD(F12*) with (aug-)cc-pVTZ-F12 basis sets on the one hand, and (T) extrapolated from conventional CCSD(T)/heavy-aug-cc-pV{D,T}Z on the other hand. Implications for earlier benchmarks on the larger S66×8 problem set in particular, and for accurate calculations on non-covalent interactions in general, are discussed. At a slight cost in accuracy, (T) can be considerably accelerated by using sano-V{D,T}Z+ basis sets, whereas half-counterpoise CCSD(F12*)(T)/cc-pVDZ-F12 offers the best compromise between accuracy and computational cost.

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