Benchmarking Basis Sets for Density Functional Theory Thermochemistry Calculations: Why Unpolarized Basis Sets and the Polarized 6-311G Family Should Be Avoided

Pitman, Samuel J.; Evans, Alicia K.; Ireland, Robbie T.; Lempriere, Felix; McKemmish, Laura K.

doi:10.1021/acs.jpca.3c05573

Cited by 10 publications

(4 citation statements)

References 93 publications

(132 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“… 22 In this context, the Density Functional Theory (DFT) calculations, specifically the 6-311G (d,p) basis set at the B3LYP level were carried out. 57–59 …”

Section: Resultsmentioning

confidence: 99%

“…22 In this context, the Density Functional Theory (DFT) calculations, specically the 6-311G (d,p) basis set at the B3LYP level were carried out. [57][58][59] The highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) are two popular quantum chemical parameters. 60 The energies of these molecular orbitals, also known as frontier molecular orbitals (FMOs), are important parameters for predicting the reactivity of a chemical species.…”

Section: Characterizationmentioning

confidence: 99%

See 1 more Smart Citation

Novel isatin–triazole based thiosemicarbazones as potential anticancer agents: synthesis, DFT and molecular docking studies

Mushtaq,

Asif,

Humayun

et al. 2024

RSC Adv.

View full text Add to dashboard Cite

show abstract

“… 22 In this context, the Density Functional Theory (DFT) calculations, specifically the 6-311G (d,p) basis set at the B3LYP level were carried out. 57–59 …”

Section: Resultsmentioning

confidence: 99%

Section: Characterizationmentioning

confidence: 99%

Novel isatin–triazole based thiosemicarbazones as potential anticancer agents: synthesis, DFT and molecular docking studies

Mushtaq,

Asif,

Humayun

et al. 2024

RSC Adv.

View full text Add to dashboard Cite

show abstract

“…Implicit solvation effects (methanol, epsilon = 32.613) at 373.15 K were included using the CPCM model as implemented in the Gaussian 09 package . Subsequently, single-point calculations were performed on the optimized structures using a triple-ζ quality 6-311++G** basis set for nonmetallic elements, which was earlier reported to produce accurate thermochemistry data with lower basis set superposition error when used in conjugation with M06-2X . Further, LANL2TZ(f) basis set , with the associated pseudopotential was used to describe the Ir atom.…”

Section: Mechanistic Studiesmentioning

confidence: 99%

Reductive Aminomethylation Using Ammonium Formate and Methanol as N1 and C1 Source: Direct Synthesis of Mono- and Di-Methylated Amines

Borthakur,

Nandi,

Bilora

et al. 2024

ACS Catal.

View full text Add to dashboard Cite

An Ir(III) complex catalyzed single and dual reductive amination followed by N-methylation of aldehydes and ketones to synthesize N,N-dimethyl as well as N-methyl tertiary amines, respectively, utilizing ammonium formate and methanol as N1 and C1 sources is reported. The protocol was efficiently extended to a tandem reductive amination/N-methylation/cyclization of keto acids/esters leading to N-methyl lactams. A broad substrate scope, synthesis of bioactive molecules, was also demonstrated. Control experiments, kinetic studies, and DFT calculations were performed based on which a plausible mechanism is proposed.

show abstract

“…We would especially like to point out here the problematic nature of the 6-311G family: it is merely of valence double-ζ quality instead of the intended valence triple-ζ quality [9], and can also lead to peculiar chemistries [10]. Unfortunately, this is still not widely appreciated, as demonstrated by a recent benchmark study [11].…”

Section: Introductionmentioning

confidence: 98%

Importance profiles. Visualization of atomic basis set requirements

Lehtola

2024

Electron. Struct.

View full text Add to dashboard Cite

Recent developments in fully numerical methods promise interesting opportunities for new, compact atomic orbital (AO) basis sets that maximize the overlap to fully numerical reference wave functions, following the pioneering work of Richardson and coworkers from the early 1960s. Motivated by this technique, we suggest a way to visualize the importance of AO basis functions employing fully numerical wave functions computed at the complete basis set (CBS) limit: the importance of a normalized AO basis function |α⟩ centered on somenucleus can P be visualized by projecting |α⟩ on the set of numerically represented occupied orbitals |ψi ⟩ as I0 (α) = i ⟨α|ψi ⟩⟨ψi |α⟩. Choosing α to be a continuous parameter describing the orbital basis, such as the exponent of a Gaussian-type orbital (GTO) or Slater-type orbital (STO) basis function, one is then able to visualize the importance of various functions. The proposed visualization I0 (α) has the important property 0 ≤ I0 (α) ≤ 1 which allows unambiguous interpretation. We also propose a straightforward generalization of the importance profile for polyatomic appliations I(α), in which the importance of a test function |α⟩ is measured as the increase in projection from the atomic minimal basis. We exemplify the methods with importance profiles computed for atoms from the first three rows, and for a set of chemically diverse diatomic molecules. We find that the importance profile offers a way to visualize the atomic basis set requirements for a given system in an a priori manner, provided that a fully numerical reference wave function is available.

show abstract

Benchmarking Basis Sets for Density Functional Theory Thermochemistry Calculations: Why Unpolarized Basis Sets and the Polarized 6-311G Family Should Be Avoided

Cited by 10 publications

References 93 publications

Novel isatin–triazole based thiosemicarbazones as potential anticancer agents: synthesis, DFT and molecular docking studies

Novel isatin–triazole based thiosemicarbazones as potential anticancer agents: synthesis, DFT and molecular docking studies

Reductive Aminomethylation Using Ammonium Formate and Methanol as N1 and C1 Source: Direct Synthesis of Mono- and Di-Methylated Amines

Importance profiles. Visualization of atomic basis set requirements

Contact Info

Product

Resources

About