Performance of B3LYP Density Functional Methods for a Large Set of Organic Molecules

Tirado‐Rives, Julian; Jorgensen, William L.

doi:10.1021/ct700248k

Cited by 1,019 publications

(566 citation statements)

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“…The M062X functional appears to offer comparable isomerization energy prediction performance to the best performing currently available dispersion corrected functionals against this benchmark dataset.The performance of various levels of quantum chemical methods for estimating the isomerization energies (∆ isom E) and enthalpies (∆ isom H) of organic compounds has been the focus of a number of investigations over the past several years [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15]. This attention is primarily driven by the poor performance of many popular density functionals -most notably the B3LYP functional -with regard to these types of intramolecular rearrangements.…”

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confidence: 99%

Performance of the M062X density functional against the ISOL set of benchmark isomerization energies for large organic molecules

Rayne

Forest

2010

Nat Prec

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Gas phase standard state (298.15 K, 1 atm) isomerization energies (∆ isom E) were calculated using the M062X functional with the QZVP, 6-311++G(d,p), 6-311++G(2d,2p), and cc-pVTZ basis sets against the 24 reactions in the ISOL set of benchmark isomerization energies for large organic molecules. The M062X functional appears to offer comparable isomerization energy prediction performance to the best performing currently available dispersion corrected functionals against this benchmark dataset.The performance of various levels of quantum chemical methods for estimating the isomerization energies (∆ isom E) and enthalpies (∆ isom H) of organic compounds has been the focus of a number of investigations over the past several years [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15]. This attention is primarily driven by the poor performance of many popular density functionals -most notably the B3LYP functional -with regard to these types of intramolecular rearrangements. Several new types of functionals and corrections have been developed in response to these reported theoretical shortcomings. However, prior ∆ isom H/∆ isom E benchmarking efforts have concentrated on relatively small molecules (<8 heavy atoms).Recently, Huenerbein et al. [15] have proposed the ISOL set of 24 isomerization reactions for large organic compounds (Figure 1). In their benchmarking study, the authors obtained reference ∆ isom E at the SCS-MP3/CBS level on B97D/TZVP optimized structures. Based on previous efforts showing the M062X density functional performs well for computing ∆ isom H/∆ isom E of smaller organic molecules [6,[10][11][12], in the current work we assess the performance of this functional for calculating ∆ isom E for the ISOL benchmark set.Single point calculations were performed using Gaussian 09 [16] and the M062X density functional [17] with the QZVP [18], 6-311++G(d,p) and 6-311++G(2d,2p) [19][20][21][22][23], and cc-pVTZ [24,25] basis sets on the B97D/TZVP optimized geometries from the ISOL set in Huenerbein et al. [15], and corresponding ∆ isom E were calculated along with associated method specific error metrics against the reference SCS-MP3/CBS ∆ isom E (Table 1) (QZVP,p), and 6-311++G(2d,2p)) or two (cc-pVTZ) outliers present with maximum absolute deviations ranging from 13.8 to 17.8 kcal mol −1 depending on the basis set, also similar to that of the PBE0 (MAXD=9.1 kcal mol −1 ; 0 outliers), B2GP-PLYP-D (MAXD=11.5 kcal mol −1 ; 1 outlier), BMK-D (MAXD=17.1 kcal mol −1 ; 1 outlier), and PW6B95-D (MAXD=11.9 kcal mol −1 ;

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confidence: 99%

Performance of the M062X density functional against the ISOL set of benchmark isomerization energies for large organic molecules

Rayne

Forest

2010

Nat Prec

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“…Structural and electronic parameters of the OAQX quinoxaline derivative were obtained in gas phase by using B3LYP method 30 combined with 6-311++G(d,p) basis set method in a Gaussian Program. 31 Atomic charges were calculated from the Chelpg method 32 which allowed for building a potential energy surface for the referred inhibitor.…”

Section: Computational Detailsmentioning

confidence: 99%

“…The method employed was the hybrid B3LYP, 30 which has been found to present good results for understanding the inhibitory ability of several compounds, 33 combined with 6-311++G(d,p) basis set. DFT calculations were performed in gas phase using a Gaussian Program.…”

Section: Computational Calculationsmentioning

confidence: 99%

Experimental and Theoretical Analysis of an Oxazinoquinoxaline Derivative for Corrosion Inhibition of Aisi 1018 Steel

et al. 2017

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The inhibitory ability of an oxazinoquinoxaline derivative (OAQX) against the corrosion of AISI 1018 mild steel induced by aqueous 0.6 mol L -1 NaCl solution is herein evaluated. Linear polarization resistance studies showed the inhibitory efficiency of OAQX varying from 62.75% to 75.93% with OAQX concentration ranged from 0.259 x 10 -4 mol L -1 to 3.243 x 10 -4 mol L -1 . Aiming at to investigate the Tafel curves on the OAQX electrochemical behavior at saline (0.6 mol L -1 NaCl) aqueous media the linear Tafel segments of anodic and cathodic curves were extrapolated to the intersection point which afforded corrosion potential (E corr ) and corrosion current density (i corr ) data. By applying Tafel approach the efficiency of OAQX ranges from 55.30% to 87.60%. In both analysis Langmuir isotherm lead to optimized adsorption parameter. The adsorption mechanism of OAQX is proposed from FTIR experiments and quantum calculations. The theoretical employed method is hybrid B3LYP combined with 6-311++G(d,p). Theoretical results showed OAQX as a promising inhibitor that form a stable protective metal-ligand film on metal surfaces, and differs from several heterocyclic compounds due to its solubility in small amount of DMSO (0.627 x 10 -4 mol L -1 ) which is resistant to a saline aqueous media (0.6 mol L -1 NaCl).Keywords: oxazinoquinoxaline derivative; corrosion inhibitor; linear polarization resistance; FTIR analysis; modeling studies. INTRODUÇÃOCorrosion is one of the main problems found in several industrial processes since it leads to material failure and this damage cause several consequences, including pollution, risks of accidents and financial losses. [1][2][3][4][5] Mild steels have been extensively employed in many industrial fields due to their interesting properties, easy fabrication and low cost. 6 However, they are sensitive to corrosion phenomenon, and become an environmental problem. In this sense, it is important to focuses on the demand for fossil fuels from which a major application of mild steels arrives from their use in the petroleum industry. Since the largest oil sources are located underground in oceans and seas, corrosion of these materials by saline conditions has been attracting considerable attention. [7][8][9][10] The addition of a corrosion inhibitor in the corrosive medium is one of the most common approaches to control corrosion process. 11 In this context, since mild steels are basically composed of metallic atoms (iron, manganese, copper, among others) the choice of a corrosion inhibitor especially comes from its electron donation ability or electrostatic interaction. The chemical structure of organic compounds contain elements like oxygen, sulfur, nitrogen as well as π bonds, which shows high electron density. In fact, heterocyclic compounds containing nitrogen, oxygen sulfur, and phosphorous have been extensively reported for their effectiveness in this field. 2,4,[12][13][14][15][16][17][18][19][20][21][22][23][24][25] Such important characteristic contributes to the adsorption phenom...

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“…51 Thermal corrections to Gibbs energies have been calculated at the same level of theory using the rigid rotor/harmonic oscillator model. All energies are reported at 298.15 K. Improved energetics have been calculated using the double hybrid B2K-PLYP/6-311+G(3df,2p) 52 and B2-PLYP/aug-def2-TZVPP methods, 53 which combine exact HF exchange with an MP2-like correlation to a DFT calculation (the corresponding energies are included in ESI †).…”

Section: Computational Detailsmentioning

confidence: 99%

The chemical fate of paroxetine metabolites. Dehydration of radicals derived from 4-(4-fluorophenyl)-3-(hydroxymethyl)piperidine

et al. 2013

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Quantum chemical calculations have been used to model reactions which are important for understanding the chemical fate of paroxetine-derived radicals in the environment. In order to explain the experimental observation that the loss of water occurs along the ( photo)degradation pathway, four different mechanisms of radical-induced dehydrations have been considered. The elimination of water from the Ncentered radical cation, which results in the formation of an imine intermediate, has been calculated as the most feasible process. The predicted energy barrier (ΔG # 298 = 98.5 kJ mol −1 ) is within the barrier limits set by experimental measurements. All reaction intermediates and transition state structures have been calculated using the G3(MP2)-RAD composite procedure, and solvent effects have been determined using a mixed (cluster/continuum) solvation model. Several new products, which comply with the available experimental data, have been proposed. These structures could be relevant for the chemical fate of antidepressant paroxetine, but also for biologically and environmentally related substrates.

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Performance of B3LYP Density Functional Methods for a Large Set of Organic Molecules

Cited by 1,019 publications

References 52 publications

Performance of the M062X density functional against the ISOL set of benchmark isomerization energies for large organic molecules

Performance of the M062X density functional against the ISOL set of benchmark isomerization energies for large organic molecules

Experimental and Theoretical Analysis of an Oxazinoquinoxaline Derivative for Corrosion Inhibition of Aisi 1018 Steel

The chemical fate of paroxetine metabolites. Dehydration of radicals derived from 4-(4-fluorophenyl)-3-(hydroxymethyl)piperidine

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