Theoretical prediction of linear free energy relationships using proton nucleomers

Macchia, Giovanni La; Gagliardi, Laura; Carlson, Geoffrey; Jay, Ashley N.; Davis, Erik; Cramer, Christopher J.

doi:10.1002/poc.1297

Cited by 6 publications

(9 citation statements)

References 49 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Calculations use the development version of the Gaussian electronic structure program, modified to allow fractional nuclear charges and tunable nuclear exponents . Test calculations combining a noninteger point charge and a “ghost atom” as described in ref precisely reproduce the H* results. Most calculations follow ref using generalized Kohn–Sham density functional theory with the M05-2X approximate exchange–correlation functional and expanding the noninteracting reference system’s orbitals in the 6-31+G(d) basis set. − Some calculations use second-order many-body perturbation theory (MP2) in the aug-cc-pVDZ basis .…”

Section: Methodsmentioning

confidence: 69%

“…This is consistent with the ρ′ = −12.5 kcal/mol, R = −0.976 found in B3LYP/6-31+G(d,p) calculations on para-substituted benzoic acids. 30 Given this ρ′, we then fit ΔE(H*) − ΔE(H) = ρ′σ m (H*) to gas-phase M05-2X/6-31+G(d) calculations on meta H* substituted benzoic acid. We find σ m (H*) = 5.709(Z* − 1).…”

Section: Methodsmentioning

confidence: 99%

“…Rauk and co-workers used H* to explore ligand electronegativity effects in PH 5 . Cramer and co-workers applied these “proton nucleomers” to a wide range of linear free energy relationships . Nuclear charge scaling has also been used in other contexts, including cluster simulations and studies of density-driven and fractional charge errors in density functional theory.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Tunable Fictitious Substituent Effects on the π–π Interactions of Substituted Sandwich Benzene Dimers

2014

View full text Add to dashboard Cite

Substituent effects on the π-π interactions of aromatic rings are a topic of much recent debate. Real substituents give a complicated combination of inductive, resonant, dispersion, and other effects. To help partition these effects, we present calculations on fictitious "pure" σ donor/acceptor substituents, hydrogen atoms with nuclear charges other than 1. "Pure" σ donors with nuclear charge <1 weaken π-π stacking in the sandwich benzene dimer. This result is consistent with the electrostatic model of Hunter and Sanders, and different from real substituents. Calculated inductive effects are largely additive and transferable, consistent with a local direct interaction model. A second series of fictitious substituents, neutral hydrogen atoms with an artificially broadened nuclear charge distribution, give similar trends though with reduced additivity. These results provide an alternative perspective on substituent effects in noncovalent interactions.

show abstract

Section: Methodsmentioning

confidence: 69%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Tunable Fictitious Substituent Effects on the π–π Interactions of Substituted Sandwich Benzene Dimers

2014

View full text Add to dashboard Cite

show abstract

“…A medida que sea más alta la magnitud de σ mayor será su capacidad electrónica. 15 Rev Soc Quím Perú. 85(2) 2019…”

Section: Efecto Sustituyenteunclassified

Estudio Teórico De La Actividad Antioxidante De Compuestos Aromáticos Con Bases De Schiff Heterocíclicas Sustituidos en Posiciones Meta Y Para

García

Lezama

Pumachagua

2018

rsqp

View full text Add to dashboard Cite

En el presente estudio se analiza la relación que presenta 11 compuestos aromáticos con bases de Schiff heterocíclicas y sustituidos en posición meta y para con la actividad antioxidante, aplicando el método UB3LYP/6-311G(d,p) dentro de la teoría del funcional de densidad. Determinamos los parámetros: entalpía de disociación de enlace (BDE), potencial de ionización (IP), entalpía de disociación de protones (PDE), afinidad de protones (PA), entalpía de transferencia de electrones (ETE) y energía de estabilización de radicales (RSE), todos en fase gaseosa. Los resultados muestran que los sustituyentes electrodonadores aumentan BDE cuando se encuentran en posición para, IP en posición meta y para y ETE en posición para. Además, los electroatractores causan un aumento en PDE y PA en posición meta y para.

show abstract

“…We approximate real support and promoter effects using fictitious point charges with noninteger charge δ . Noninteger point charges have been used to simulate semiconductor doping, “pure” inductive substituent effects, and linear free energy relationships, as link atoms in cluster simulations, and in fundamental studies of density‐driven and fractional‐charge errors. We embed these fictitious point charges into a finite cluster model of an unpromoted catalyst, for which we have precomputed the reaction mechanism.…”

Section: Introductionmentioning

confidence: 99%

Tunable model promoters in DFT simulations of catalysts

et al. 2019

View full text Add to dashboard Cite

Promoter atoms can tune a catalyst's activity and selectivity by transferring charge to and from the active site. Rational design of promoted catalysts, using density functional theory calculations, is today limited by the need to simulate many catalyst and promoter configurations. We present a simple approximation that rapidly captures some trends in promoter effects, at a cost of complexity comparable with simulating unpromoted catalysts. Negative (positive) noninteger point charges introduced into the catalyst simulate how electropositive (electronegative) promoters might affect each predicted intermediate. Calculations return Sabatier plots, relating promoters' predicted efficacy to readily measured properties such as catalyst work functions. We illustrate our approach for two reactions associated with the Fischer–Tropsch process, hydrogen–deuterium scrambling, and carbon monoxide dissociation over ruthenium. Consistent with experiment, electropositive promoters are predicted to accelerate hydrogen scrambling and unassisted CO dissociation. Simulations also provide a new prediction: electronegative promoters accelerate hydrogen‐assisted CO dissociation over hydrogen‐precovered surfaces by stabilizing the initial CO adsorption. © 2019 Wiley Periodicals, Inc.

show abstract

Theoretical prediction of linear free energy relationships using proton nucleomers

Cited by 6 publications

References 49 publications

Tunable Fictitious Substituent Effects on the π–π Interactions of Substituted Sandwich Benzene Dimers

Tunable Fictitious Substituent Effects on the π–π Interactions of Substituted Sandwich Benzene Dimers

Estudio Teórico De La Actividad Antioxidante De Compuestos Aromáticos Con Bases De Schiff Heterocíclicas Sustituidos en Posiciones Meta Y Para

Tunable model promoters in DFT simulations of catalysts

Contact Info

Product

Resources

About