The charge-asymmetric nonlocally determined local-electric (CANDLE) solvation model

Sundararaman, Ravishankar; Goddard, William A.

doi:10.1063/1.4907731

Cited by 188 publications

(250 citation statements)

References 33 publications

Supporting

Mentioning

247

Contrasting

Order By: Relevance

“…27 Fig. 1 shows that the CANDLE capacitance agrees well with experiment for potentials negative of the PZC, but underestimates it similarly to the other solvation models for positive potentials.…”

supporting

confidence: 53%

“…Left: Surface charge as a function of electrode potential at 0.1 M ionic concentration for LinearPCM 17 , CANDLE 27 , NonlinearPCM 17 , and the SCCS 33,34 solvation models, compared to experimental data from Hamelin 25 for NaClO 4 and Valette 26 for KPF 6 . Right: Bound charge in the NonlinearPCM continuum solvent at 0.6 V above PZC.…”

Section: Figmentioning

confidence: 99%

“…27. Briefly, we use the JDFTx code, 28 with the PBE exchange-correlation functional, 29 the GBRV ultrasoft pseudopotential set 30 at its recommended plane-wave cutoffs of 20 E h for orbitals and 100 E h for charge density.…”

mentioning

confidence: 99%

See 2 more Smart Citations

Evaluating continuum solvation models for the electrode-electrolyte interface: Challenges and strategies for improvement

2017

Self Cite

View full text Add to dashboard Cite

Ab initio modeling of electrochemical systems is becoming a key tool for understanding and predicting electrochemical behavior. Development and careful benchmarking of computational electrochemical methods are essential to ensure their accuracy. Here, using charging curves for an electrode in the presence of an inert aqueous electrolyte, we demonstrate that most continuum models, which are parameterized and benchmarked for molecules, anions, and cations in solution, undersolvate metal surfaces, and underestimate the surface charge as a function of applied potential. We examine features of the electrolyte and interface that are captured by these models, and identify improvements necessary for realistic electrochemical calculations of metal surfaces. Finally, we reparameterize popular solvation models using the surface charge of Ag(100) as a function of voltage to find improved accuracy for metal surfaces without significant change in utility for molecular and ionic solvation.

show abstract

supporting

confidence: 53%

Section: Figmentioning

confidence: 99%

See 1 more Smart Citation

Evaluating continuum solvation models for the electrode-electrolyte interface: Challenges and strategies for improvement

2017

Self Cite

View full text Add to dashboard Cite

show abstract

“…In contrast, more negative U has little impact on ΔE B of CO, because charges barely transfer during CO adsorption. To validate this, the charge transfers during CO adsorption were calculated under fixed applied potentials by optimizing the number of electrons (N e ) along the reaction path (27) within the framework of joint density functional theory (28), and the solvation effects was handled by the charge-asymmetric nonlocally determined local-electric implicit model (29). We find that, for increasingly negative U, ΔE B of H* increases, and finally matches the CO binding at U = −0.69 V (RHE).…”

Section: Resultsmentioning

confidence: 99%

Full atomistic reaction mechanism with kinetics for CO reduction on Cu(100) from ab initio molecular dynamics free-energy calculations at 298 K

Cheng

Xiao

Goddard

2017

Proc. Natl. Acad. Sci. U.S.A.

Self Cite

444

579

View full text Add to dashboard Cite

A critical step toward the rational design of new catalysts that achieve selective and efficient reduction of CO 2 to specific hydrocarbons and oxygenates is to determine the detailed reaction mechanism including kinetics and product selectivity as a function of pH and applied potential for known systems. To accomplish this, we apply ab initio molecular metadynamics simulations (AIMμD) for the water/Cu(100) system with five layers of the explicit solvent under a potential of −0.59 V [reversible hydrogen electrode (RHE)] at pH 7 and compare with experiment. From these free-energy calculations, we determined the kinetics and pathways for major products (ethylene and methane) and minor products (ethanol, glyoxal, glycolaldehyde, ethylene glycol, acetaldehyde, ethane, and methanol). For an applied potential (U) greater than −0.6 V (RHE) ethylene, the major product, is produced via the Eley-Rideal (ER) mechanism using H 2 O + e -. The rate-determining step (RDS) is C-C coupling of two CO, with ΔG ‡ = 0.69 eV. For an applied potential less than −0.60 V (RHE), the rate of ethylene formation decreases, mainly due to the loss of CO surface sites, which are replaced by H*. The reappearance of C 2 H 4 along with CH 4 at U less than −0.85 V arises from *CHO formation produced via an ER process of H* with nonadsorbed CO (a unique result). This *CHO is the common intermediate for the formation of both CH 4 and C 2 H 4 . These results suggest that, to obtain hydrocarbon products selectively and efficiency at pH 7, we need to increase the CO concentration by changing the solvent or alloying the surface.reaction mechanism | electrocatalysis | copper | QM metadynamics | free-energy reaction barriers

show abstract

“…G solvation = G electrostatic +G dispersion-repulsion +G cavitation Nevertheless, in SMD (Density-based Solvation Model), 26 the process of solvation free energy is completely different than PCM model. This model involves complete solute electron density without considering partial atomic charges.…”

Section: C-n Bandsmentioning

confidence: 99%

Untitled

Khalid¹,

Ali²,

Aslam³

et al. 2017

IJPSR

View full text Add to dashboard Cite

N-heterocyclic compounds have extensive biological and pharmaceutical applications. 8-Hydroxyquinoline (8-HQ) also plays a significant role in many fields of life. The excellent biological significance of the 8-HQ prompted us to extend the DFT based studies. The frontier molecular orbitals (FMOs), UV-VIS and solvation model based studies remained unknown. Therefore, we intended to study the natural bond orbital, FMOs, UV-VIS, thermodynamic properties and medium influence on solvation energies, dipole moment, FT-IR and FT-Raman using polarizable continuum model (PCM) and density-based solvation model (SMD). The electronic properties of molecule were calculated by M06-2X/6-31G (d,P) and B3LYP/6-31G (d,p) level of theories. The solvent influence on the geometric parameters, FT-IR and FT-Raman were studied by B3LYP /6-31G(d) method. A good correspondence is found between the optimized parameters and the reported X-ray data. Natural bond orbital reveals that the maximum stabilization energy reached up to 39.64kJ/mol which is responsible for extra stability of the molecule. In solvated 8-HQ, a significant medium effects on FT-IR and FT-Raman intensities is observed. The intensities enhanced from gas to solvent phase. The solvation free energies are found to be -28.710 and -39.456 kJ/mol in PCM and SMD models respectively. FMOs suggested that this molecule contain less hardness and larger softness values. These findings reveal that the molecule might be bioactive.

show abstract

The charge-asymmetric nonlocally determined local-electric (CANDLE) solvation model

Cited by 188 publications

References 33 publications

Evaluating continuum solvation models for the electrode-electrolyte interface: Challenges and strategies for improvement

Evaluating continuum solvation models for the electrode-electrolyte interface: Challenges and strategies for improvement

Full atomistic reaction mechanism with kinetics for CO reduction on Cu(100) from ab initio molecular dynamics free-energy calculations at 298 K

Untitled

Contact Info

Product

Resources

About