Assessing the Applicability of the Geometric Counterpoise Correction in B2PLYP/Double-ζ Calculations for Thermochemistry, Kinetics, and Noncovalent Interactions

Mehta, Nisha; Goerigk, Lars

doi:10.1071/ch21133

Cited by 4 publications

(4 citation statements)

References 147 publications

(164 reference statements)

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“…Analogous association has been used to provide a good description of similar molecular systems and to reproduce their spectra (Mehandzhiyski et al, 2015), (Sert et al, 2015). Before optimization, the BSEE counterpoise correction method was used to adjust the interaction energies between the potassium cation and the sorbate anion (Mehta & Goerigk, 2021). The structure of the compound was optimized without any structural constraints and the inexistence of negative frequencies values proved that the obtained structure was in the minima energy state.…”

Section: Optimization Of the Molecular Structurementioning

confidence: 99%

Comparative Experimental and Theoretical Study on the Structure of Potassium 2,4-Hexadienoate: Structure-Activity Relationship

TAFERGUENNIT,

KICHOU,

HANK

2023

EPSTEM

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For the first time, a density functional theory (DFT) study was conducted on the structure of a well-known antibacterial agent namely potassium 2,4-Hexadienoate, in order to elucidate its vibrational, electronic and reactivity proprieties. Structure optimization was performed using three common hybrid functionals (DFT/ B3LYP-D3; DFT/ M05-2X and DFT/M06-2X) to identify the suitable functional. Geometric parameters, IR and UV-vis spectra were well reproduced when using DFT/M06-2X with 6-311(d)G+ basis set (R2 = 0.99913). The assimilation of IR frequencies has been achieved using potential energy distribution (PED)analysis at M06-2X/6-311(d) G + level. Time-dependent density functional theory (TD-DFT) and natural bond orbital (NBO) analysis were realized to identify the excited states of 2,4-Hexadienoate anion in the liquid phase, using the solute electron density solvation model (SMD). Moreover, reactive sites in the molecule were localized by molecular electrostatic potential (MEP) analysis. Highest Occupied Molecular Orbitals (HOMO), lowest Unoccupied Molecular Orbitals (LUMO) and energy gap (HOMO-LUMO gap), were used to calculate global reactivity descriptors (GRDs), according to the frontier molecular orbitals (FMO) theory, the resulting values were analyzed to explore the chemical reactivity of the molecule and elucidate the structure-activity relationship.

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Section: Optimization Of the Molecular Structurementioning

confidence: 99%

Comparative Experimental and Theoretical Study on the Structure of Potassium 2,4-Hexadienoate: Structure-Activity Relationship

TAFERGUENNIT,

KICHOU,

HANK

2023

EPSTEM

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“…The 3c approach, which was initially proposed for a minimal basis set Hartree–Fock (HF) method (HF-3c), has also recently been extended to triple-ζ basis set DFT methods (B97-3c and r 2 SCAN-3c). Several other methodologies based on DFT have been proposed in the literature, − and this underscores the interest in developing computationally inexpensive DFT-based methods for modeling large molecular systems.…”

Section: Introductionmentioning

confidence: 99%

Small-Basis Set Density-Functional Theory Methods Corrected with Atom-Centered Potentials

Prasad

Otero-de-la-Roza

DiLabio

2022

J. Chem. Theory Comput.

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Density functional theory (DFT) is currently the most popular method for modeling noncovalent interactions and thermochemistry. The accurate calculation of noncovalent interaction energies, reaction energies, and barrier heights requires choosing an appropriate functional and, typically, a relatively large basis set. Deficiencies of the density-functional approximation and the use of a limited basis set are the leading sources of error in the calculation of noncovalent and thermochemical properties in molecular systems. In this article, we present three new DFT methods based on the BLYP, M06-2X, and CAM-B3LYP functionals in combination with the 6-31G* basis set and corrected with atom-centered potentials (ACPs). ACPs are one-electron potentials that have the same form as effective-core potentials, except they do not replace any electrons. The ACPs developed in this work are used to generate energy corrections to the underlying DFT/basis-set method such that the errors in predicted chemical properties are minimized while maintaining the low computational cost of the parent methods. ACPs were developed for the elements H, B, C, N, O, F, Si, P, S, and Cl. The ACP parameters were determined using an extensive training set of 118655 data points, mostly of complete basis set coupled-cluster level quality. The target molecular properties for the ACP-corrected methods include noncovalent interaction energies, molecular conformational energies, reaction energies, barrier heights, and bond separation energies. The ACPs were tested first on the training set and then on a validation set of 42567 additional data points. We show that the ACP-corrected methods can predict the target molecular properties with accuracy close to complete basis set wavefunction theory methods, but at a computational cost of double-ζ DFT methods. This makes the new BLYP/6-31G*-ACP, M06-2X/6-31G*-ACP, and CAM-B3LYP/ 6-31G*-ACP methods uniquely suited to the calculation of noncovalent, thermochemical, and kinetic properties in large molecular systems.

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“…The 3c approach, which was initially proposed for a minimal basis set Hartree-Fock (HF) method (HF-3c 28 ), has also recently been extended to triple-ζ basis set DFT methods (B97-3c 32 and r 2 SCAN-3c 33 ). Several other methodologies based on DFT have been proposed in the literature [34][35][36][37][38][39][40] , and this underscores the interest in developing computationally inexpensive DFT based methods for modeling large molecular systems.…”

Section: Introductionmentioning

confidence: 99%

Small basis set density-functional theory methods corrected with atom-centered potentials

Prasad

Otero-de-la-Roza

DiLabio

2022

Preprint

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Density-functional theory (DFT) is currently the most popular method for modeling non-covalent interactions and thermochemistry. The accurate calculation of non-covalent interaction energies, reaction energies, and barrier heights requires choosing an appropriate functional and, typically, a relatively large basis set. Deficiencies of the density-functional approximation and the use of a limited basis set are the leading sources of error in the calculation of non-covalent and thermochemical properties in molecular systems. In this article, we present three new DFT methods based on the BLYP, M062X and CAM-B3LYP functionals in combination with the 6-31G* basis set and corrected with atom-centered potentials (ACPs). ACPs are one-electron potentials that have the same form as effective-core potentials, except they do not replace any electrons. The ACPs developed in this work are used to generate energy corrections to the underlying DFT/basis-set method such that the errors in predicted chemical properties are minimized while maintaining the low computational cost of the parent methods. ACPs were developed for the elements H, B, C, N, O, F, Si, P, S, and Cl. The ACP parameters were determined using an extensive training set of 118,655 data points, mostly of complete basis set coupled-cluster level quality. The target molecular properties for the ACP-corrected methods include non-covalent interaction energies, molecular conformational energies, reaction energies, barrier heights, and bond separation energies. The ACPs were tested first on the training set and then on a validation set of 42,567 additional data points. We show that the ACP-corrected methods can predict the target molecular properties with accuracy close to complete basis set wavefunction theory methods, but at a computational cost of double-ζ DFT methods. This makes the new BLYP/6-31G*-ACP, M062X/6-31G*-ACP, and CAM-B3LYP/6-31G*-ACP methods uniquely suited to the calculation of non-covalent, thermochemical, and kinetic properties in large molecular systems.

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Assessing the Applicability of the Geometric Counterpoise Correction in B2PLYP/Double-ζ Calculations for Thermochemistry, Kinetics, and Noncovalent Interactions

Cited by 4 publications

References 147 publications

Comparative Experimental and Theoretical Study on the Structure of Potassium 2,4-Hexadienoate: Structure-Activity Relationship

Comparative Experimental and Theoretical Study on the Structure of Potassium 2,4-Hexadienoate: Structure-Activity Relationship

Small-Basis Set Density-Functional Theory Methods Corrected with Atom-Centered Potentials

Small basis set density-functional theory methods corrected with atom-centered potentials

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