Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways

Mathew, Kiran; Sundararaman, Ravishankar; Letchworth‐Weaver, Kendra; Arias, T. A.; Hennig, Richard G.

doi:10.1063/1.4865107

Cited by 1,854 publications

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“…2 kcal mol −1 (78). This approach expresses the dispersion contribution to the solvation free energy as being proportional to the exposed molecular surface area (27,29), and so we express the change in solvation energy on SAM formation as ΔE s = ΔE s,SAM − ΔE s,P − ΔE s,HOPG = −αðA SAM − A P − A HOPG Þ [6] where ΔE s,SAM , ΔE s,P , and ΔE s,HOPG are the solvation energies of the SAM, the porphyrin in solution, and a solvated bare HOPG surface, respectively, and A SAM , A P , and A HOPG are the corresponding exposed surface areas. The proportionality constant α = 0.0866 kcal mol −1 Å −2 is fitted to B3LYP/6-31G* calculated data for the optimized structures of C 11 P and C 19 P. All exposed surface areas are evaluated using the solvent-excluded surface obtained using van der Waals radii of 1.55 Å, 1.7 Å, and 1.2 Å for N, C, and H, respectively, and the solvent "radius" is taken to be 2.2 Å.…”

Section: Methodsmentioning

confidence: 99%

“…Only for this structural motif were the calculations performed alternatively, optimizing the energy in the presence of the solvent. Note that an implementation of this type of optimization (without a solvent-excluded-surface option) has just become available in VASP (29).…”

Section: Methodsmentioning

confidence: 99%

“…Modern methods (18)(19)(20)(21)(22)(23)(24)(25) can now describe discrete interactions well, and self-assembly processes such as molecular crystal formation (22) and host−guest chemistry (26) have now been successfully modeled. Dispersive interactions with a solvent continuum (18,27) are also now included in many codes, including Gaussian (28) and, very recently, VASP (29). Like discrete dispersion interactions, the best method for including continuum Significance First-principles free energy calculations, characterizing polymorphism of self-assembled monolayers (SAMs) of porphyrin molecules formed from solution onto graphite, are performed using efficient methods previously applied only to small-molecule reactivity.…”

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confidence: 99%

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A priori calculations of the free energy of formation from solution of polymorphic self-assembled monolayers

Reimers

Panduwinata

Visser

et al. 2015

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

110

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Modern quantum chemical electronic structure methods typically applied to localized chemical bonding are developed to predict atomic structures and free energies for meso-tetraalkylporphyrin self-assembled monolayer (SAM) polymorph formation from organic solution on highly ordered pyrolytic graphite surfaces. Large polymorphdependent dispersion-induced substrate−molecule interactions (e.g., −100 kcal mol −1 to −150 kcal mol −1 for tetratrisdecylporphyrin) are found to drive SAM formation, opposed nearly completely by large polymorph-dependent dispersion-induced solvent interactions (70-110 kcal mol −1 ) and entropy effects (25-40 kcal mol −1 at 298 K) favoring dissolution. Dielectric continuum models of the solvent are used, facilitating consideration of many possible SAM polymorphs, along with quantum mechanical/molecular mechanical and dispersion-corrected density functional theory calculations. These predict and interpret newly measured and existing high-resolution scanning tunnelling microscopy images of SAM structure, rationalizing polymorph formation conditions. A wide range of molecular condensed matter properties at room temperature now appear suitable for prediction and analysis using electronic structure calculations.self-assembled monolayers | density functional theory | dispersion | free energy | polymorphism A priori calculations of the free energies of chemical reactions using density functional theory (DFT) and/or ab initio methods are now well established for gas-phase processes (1, 2), gas surface reactions (3), and, using continuum self-consistent reaction field (SCRF) methods, for condensed phase processes also (4). Over the last few years, a major advance in computational methods has occurred, however, allowing for rapid and accurate evaluation of intermolecular dispersion interactions. This makes feasible similar SCRF calculations for physisorption, macromolecule structuring, and other self-assembly processes in condensed phases. We present the first application of this type, to our knowledge, considering the free energy of formation of various polymorphs of tetraalkylporphyrin self-assembled monolayers (SAMs) at solid/liquid interfaces on highly ordered pyrolytic graphite (HOPG) surfaces. Calculated structures and free energies are used to interpret new and existing high-resolution scanning tunneling microscopy (STM) images, focusing on the critical roles played by the dispersion interaction in driving SAM formation and by entropy and dispersion-based desolvation effects that oppose it.Calculating a priori free energies for SAM formation from solution is a significant challenge. Accurate representations of the substrate−molecule energies, the intermolecular energies, the solvent interaction energies, and the effects of solvent structure are required, a set of tasks that, with a few exceptions (see e.g., refs. 5 and 6), has remained prohibitive a priori. Alternatively, model calculations have been useful for identifying key qualitative features (7-11), whereas some full molecular dynamics si...

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

See 1 more Smart Citation

A priori calculations of the free energy of formation from solution of polymorphic self-assembled monolayers

Reimers

Panduwinata

Visser

et al. 2015

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

110

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“…47 Here, self-consistent wavefunctions were reevaluated at the GGA level in the presence of the continuum solvation field. These wavefunctions were subsequently used as input to G 0 W 0 calculations.…”

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confidence: 99%

Interface-Induced Renormalization of Electrolyte Energy Levels in Magnesium Batteries

Kumar¹,

Siegel

2016

J. Phys. Chem. Lett.

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A promising strategy for increasing the energy density of Li-ion batteries is to substitute a multivalent (MV) metal for the commonly used lithiated carbon anode. Magnesium is a prime candidate for such a MV battery due to its high volumetric capacity, abundance, and limited tendency to form dendrites. One challenge that is slowing the implementation of Mg-based batteries, however, is the development of efficient and stable electrolytes. Computational screening for molecular species having sufficiently wide electrochemical windows is a starting point for the identification of optimal electrolytes. Nevertheless, this window can be altered via interfacial interactions with electrodes. These interactions are typically omitted in screening studies, yet they have the potential to generate large shifts to the HOMO and LUMO of the electrolyte components. The present study quantifies the stability of several common electrolyte solvents on model electrodes of relevance for Mg batteries. Many-body perturbation theory calculations based on the G 0 W 0 method were used to predict shifts in a solvent's electronic levels arising from interfacial interactions. In molecules exhibiting large dipole moments, our calculations indicate that these interactions reduce the HOMO− LUMO gap by ∼25% (compared to isolated molecules). We conclude that electrode interactions can narrow an electrolyte's electrochemical window significantly, thereby accelerating redox decomposition reactions. Accounting for these interactions in screening studies presents an opportunity to refine predictions of electrolyte stability.

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“…This approach has long been used in the quantum chemistry community to study ionic and molecular solvation, 227 and similar ideas are now beginning to be adapted for solid-liquid interfaces. [228][229][230][231][232] Such polarizable continuum-based schemes can also mitigate another critical challenge for realistic simulations of electrode-electrolyte interfaces and catalytic redox electrochemistry-namely, the application of a well-defined voltage bias or photo-bias. Typically, there are two complications associated with an external bias within DFT: first, charge neutrality considerations that prevent accurate determination of a potential reference for a charged system that can be directly compared with experiments; and second, fundamental incompatibilities with the periodic boundary conditions generally employed for simulations of extended crystalline systems.…”

Section: Dft and Ground-state Techniquesmentioning

confidence: 99%

Methods of photoelectrode characterization with high spatial and temporal resolution

Esposito

Baxter

John

et al. 2015

Energy Environ. Sci.

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Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways

Cited by 1,854 publications

References 39 publications

A priori calculations of the free energy of formation from solution of polymorphic self-assembled monolayers

A priori calculations of the free energy of formation from solution of polymorphic self-assembled monolayers

Interface-Induced Renormalization of Electrolyte Energy Levels in Magnesium Batteries

Methods of photoelectrode characterization with high spatial and temporal resolution

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