2019
DOI: 10.1002/poc.3961
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Determination of the best functional and basis sets for optimization of the structure of hypervalent iodines and calculation of their first and second bond dissociation enthalpies

Abstract: Hypervalent iodines are widely used in organic chemistry, and their most important feature is the three‐center four‐electron bond. However, there have been few reports on the measurement of their bond dissociation enthalpy (BDE). Therefore, in many cases, BDE is estimated by computational calculations. However, the value of a calculated BDE usually varies depending on the choice of functional and basis set, and the best method for making an accurate evaluation of the three‐center four‐electron bond has not bee… Show more

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Cited by 30 publications
(28 citation statements)
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“…Solvation by N , N ‐dimethylacetamide (DMAc) was described by the SMD continuum solvation model in the optimizations and single‐point corrections . In benchmark studies performed on geometric and thermodynamic properties of hypervalent iodine species, the ωB97X‐D functional with valence triple‐ζ polarized basis set ranked highly . In our studies, the use of alternative basis sets (e.g., def2‐TZVPPD) to describe the I atom during geometry optimization gave unchanged geometries (Figure S6 a in the Supporting Information) and had minimal impact on the energy profiles computed at 1 m concentration and 298.15 K (Figure S6 b in the Supporting Information).…”
Section: Resultsmentioning
confidence: 99%
“…Solvation by N , N ‐dimethylacetamide (DMAc) was described by the SMD continuum solvation model in the optimizations and single‐point corrections . In benchmark studies performed on geometric and thermodynamic properties of hypervalent iodine species, the ωB97X‐D functional with valence triple‐ζ polarized basis set ranked highly . In our studies, the use of alternative basis sets (e.g., def2‐TZVPPD) to describe the I atom during geometry optimization gave unchanged geometries (Figure S6 a in the Supporting Information) and had minimal impact on the energy profiles computed at 1 m concentration and 298.15 K (Figure S6 b in the Supporting Information).…”
Section: Resultsmentioning
confidence: 99%
“…We first performed DFT calculations to increase the sizes of the data set populations. The DFT calculations were performed using Gaussian16 with MN15 28 functional and SDD 29 , 30 (for I and Se) and cc-pvTZ 31 (for the others) basis sets 19 . Structure optimizations were carried out with an ultrafine grid at 298.15 K in gas phase.…”
Section: Methodsmentioning
confidence: 99%
“…All the calculations were performed using the DFT long-range dispersion-corrected Head-Gordon hybrid functional B97XD [13,[27][28][29], as implemented in Gaussian 16 [30]. The DGDZVP basis set was used to express the wavefunction, since it has been determined to correctly describe the H-Xe elements range [31][32][33][34][35]. Solvent effects were also considered by employing both implicit method and explicit water molecules.…”
Section: Methodsmentioning
confidence: 99%