A5061017744- Advanced Chemical Physics Studies
- Spectroscopy and Quantum Chemical Studies
- Free Radicals and Antioxidants
- Photochemistry and Electron Transfer Studies
- Electrochemical Analysis and Applications
- Inorganic Fluorides and Related Compounds
- Catalysis and Oxidation Reactions
- Metal complexes synthesis and properties
- Atmospheric Ozone and Climate
- Molecular Spectroscopy and Structure
- Atmospheric chemistry and aerosols
- Molecular Junctions and Nanostructures
- Chemical and Physical Properties in Aqueous Solutions
- Ionic liquids properties and applications
- Machine Learning in Materials Science
- Advanced NMR Techniques and Applications
- Thermal and Kinetic Analysis
- Multicomponent Synthesis of Heterocycles
- Catalytic Processes in Materials Science
- Solid-state spectroscopy and crystallography
- Chemical Reaction Mechanisms
- Crystal Structures and Properties
- Synthesis and biological activity
- Electrocatalysts for Energy Conversion
- Advanced Thermodynamics and Statistical Mechanics
University of Minnesota
2007-2021
University of Minnesota System
2013-2014
Pittsburgh Supercomputing Center
2014
Minneapolis Institute of Arts
2014
Central China Normal University
2010
University of Kentucky
2010
Transylvania University
2010
The University of Texas at Austin
2003-2008
Kyung Hee University
2008
Lodz University of Technology
2008
We present a new continuum solvation model based on the quantum mechanical charge density of solute molecule interacting with description solvent. The is called SMD, where "D" stands for "density" to denote that full electron used without defining partial atomic charges. "Continuum" denotes solvent not represented explicitly but rather as dielectric medium surface tension at solute-solvent boundary. SMD universal model, "universal" its applicability any charged or uncharged in liquid which...
A summary of the technical advances that are incorporated in fourth major release Q-Chem quantum chemistry program is provided, covering approximately last seven years. These include developments density functional theory methods and algorithms, nuclear magnetic resonance (NMR) property evaluation, coupled cluster perturbation theories, for electronically excited open-shell species, tools treating extended environments, algorithms walking on potential surfaces, analysis tools, energy...
We find that vibrational contributions to a solute's free energy are in general insensitive whether the solute frequencies computed gas phase or solution. In most cases, difference is smaller than intrinsic error solvation energies associated with continuum approximation modeling, although care must be taken avoid spurious results limitations quantum-mechanical harmonic-oscillator for very low-frequency molecular vibrations. compute partition functions aqueous and carbon tetrachloride...
We propose a novel approach to deriving partial atomic charges from population analysis. The new model, called Charge Model 5 (CM5), yields class IV by mapping those obtained Hirshfeld analysis of density functional electronic charge distributions. CM5 model utilizes single set parameters derived fitting reference values the gas-phase dipole moments 614 molecular structures. An additional test (not included in parametrization) contained 107 singly charged ions with nonzero moments,...
Specialized computational chemistry packages have permanently reshaped the landscape of chemical and materials science by providing tools to support guide experimental efforts for prediction atomistic electronic properties. In this regard, structure played a special role using first-principle-driven methodologies model complex processes. Over past few decades, rapid development computing technologies tremendous increase in power offered unique chance study transformations sophisticated...
The SM6, SM8, and SMD quantum mechanical aqueous continuum solvation models are applied to predict free energies of for 61 molecules in the SAMPL1 test set described elsewhere (Guthrie. J. Phys. Chem. B 2009, 113, 4501−4507). For direct comparison other models, frozen geometries, provided by Guthrie, were used together with M06-2X density functional 6-31G(d) basis set. bulk electrostatic component energy, SM6 SM8 employ a generalized Born model that uses polarized discrete partial atomic...
A new universal continuum solvation model (where "universal" denotes applicable to all solvents), called SM8, is presented. It an implicit model, also a and it improves on earlier SMx models by including free energies of ions in nonaqueous media the parametrization. SM8 any charged or uncharged solute composed H, C, N, O, F, Si, P, S, Cl, and/or Br solvent liquid medium for which few key descriptors are known, particular dielectric constant, refractive index, bulk surface tension, acidity...
The article reviews recent developments and applications for predicting the standard reduction potentials of chemical reactions in solution.
The quantum mechanical SMD continuum universal solvation model can be applied to predict the free energy of any solute in solvent following specification various macroscopic parameters. For three ionic liquids where these descriptors are readily available, exhibits a mean unsigned error 0.48 kcal/mol for 93 energies neutral solutes and 1.10 148 water-to-IL transfer energies. Because necessary parameters not always available given liquid, we determine average values set over which...
We present a new self-consistent reaction-field implicit solvation model that employs the generalized Born approximation for bulk electrostatic contribution to free energy of solvation. The (SM) is called SM12 (where ″12″ stands 2012), and it available with two sets parameters, SM12CM5 SM12ESP. parametrization based on CM5 partial atomic charges, SM12ESP charges derived from quantum-mechanically calculated potential (ESP) (in particular, we consider ChElPG Merz-Kollman-Singh charges). was...
We present a unified treatment of solvatochromic shifts in liquid-phase absorption spectra, and we develop self-consistent state-specific vertical excitation model (called VEM) for electronic solution. discuss several other approaches to calculate excitations solution as an approximation VEM. illustrate these methods by presenting calculations the lowest excited states solutes (acetone, acrolein, coumarin 153, indolinedimethine-malononitrile, julolidine-malononitrile, methanal,...
We present a new self-consistent reaction field continuum solvation model based on the generalized Born (GB) approximation for bulk electrostatic contribution to free energy of solvation. The improves earlier SM8 by using asymmetric descreening algorithm Grycuk treat dielectric effects rather than Coulomb approximation; it will be called Solvation Model 8 with (SM8AD). SM8AD is applicable any charged or uncharged solute in solvent liquid medium which few key descriptors are known, particular...
We present results of density functional calculations for the standard reduction potential Ru3+|Ru2+ couple in aqueous solution. The metal cations are modeled as [Ru(H2O)n]q+ surrounded by continuum solvent (q = 2, 3; n 6, 18). model includes bulk electrostatic polarization well atomic surface tensions accounting deviation second or third hydration shell from bulk. After consideration 37 functionals with 5 different basis sets, it has been found that hybrid and meta provide most accurate...
First and second dissociation constants (pKa values) of oxalic acid, malonic adipic acid were computed by using a number theoretical protocols based on density functional theory both continuum solvation models mixed discrete-continuum models. We show that fully implicit (in which the entire solvent is represented dielectric continuum) fail badly for dicarboxylic acids with mean unsigned errors (averaged over six pKa 2.4-9.0 log units, depending particular model used. The use water-solute...
A physically realistic treatment of solvatochromic shifts in liquid-phase electronic absorption spectra requires a proper account for various short- and long-range equilibrium nonequilibrium solute-solvent interactions. The present article demonstrates that such can be accomplished using mixed discrete-continuum approach based on the two-time-scale self-consistent state-specific vertical excitation model (called VEM) solution. We apply this combination with time-dependent density functional...
Partial atomic charges provide the most widely used model for molecular charge polarization, and Charge Model 4 (CM4) is designed to partial that correspond an accurate distribution, even though they may be calculated with polarized double-ζ basis sets any density functional. Here we extend CM4 six additional sets, present a (CM4M) individually optimized M06 suite of functionals ten sets. These models yield class IV by mapping from those obtained Löwdin or redistributed population analyses...
We can do better! The new density functionals M11-L and M11 the SMD implicit solvation model were used to predict reduction potential–pH equilibrium diagrams (see example) for two ruthenium-based water-oxidation catalysts their derivatives in aqueous solution. observed improved accuracy transition-metal complexes opens opportunities use of theory understanding design containing transition metals. Detailed facts importance specialist readers are published as "Supporting Information". Such...
Polarizability is a key molecular property controlling induction and dispersion forces in molecules, atomic polarizabilities molecules are widely used elements both qualitative schemes for understanding interactions quantitative methods modeling them. Unfortunately, experimental probes of local polarizability not readily available. Here we predict the individual atoms functional groups variety systems, draw general specific conclusions with broad consequences. We find that same group (e.g.,...
We present a new kind of treatment the solute-solvent dispersion contribution to free energy solvation using model with state-specific polarizability (SMSSP). To evaluate contribution, SMSSP utilizes only two descriptors, namely, spherically averaged dipole solute molecule (either in its ground or excited electronic state) and refractive index solvent. The was parametrized over 643 ground-state data for 231 solutes 14 nonpolar, non-hydrogen-bonding solvents. show that is applicable both...
ADVERTISEMENT RETURN TO ISSUEPREVPerspectiveNEXTPerspective on Foundations of Solvation Modeling: The Electrostatic Contribution to the Free Energy SolvationAleksandr V. Marenich, Christopher J. Cramer*, and Donald G. Truhlar*View Author Information Department Chemistry Supercomputing Institute, University Minnesota, Minneapolis, Minnesota 55455-0431* Corresponding author e-mail: [email protected] (C.J.C.);[email (D.G.T.)Cite this: Chem. Theory Comput. 2008, 4, 6, 877–887Publication Date...
Building on the SVPE (surface and volume polarization for electrostatics) model electrostatic contributions to free energy of solvation with explicit consideration both surface effects, SMx approach including first-solvation-shell contributions, linear relationship between electric field short-range found by Chipman, we have developed a new method computing absolute aqueous energies combining semiempirical terms that account effects beyond bulk electrostatics. The is called SMVLE, elements...
Linear response (LR) Kohn-Sham (KS) time-dependent density functional theory (TDDFT), or KS-LR, has been widely used to study electronically excited states of molecules and is the method choice for large complex systems. The Tamm-Dancoff approximation TDDFT (TDDFT-TDA KS-TDA) gives results similar KS-LR alleviates instability problem near state intersections. However, KS-TDA share a debilitating feature; conical intersections reference occur in F - 1 instead correct 2 dimensions, where...
Polarization effects in aqueous and nonaqueous solutions were analyzed for nine neutral three charged organic solutes by the SM8 universal implicit solvation model class IV partial atomic charges based on Charge Model 4M (CM4M) with M06-2X density functional. The CM4M ionic corresponding clustered (supersolutes), which included one solute molecule or two solvent molecules, modeled solvents (benzene, methylene chloride, water) compared to those gas phase. use of supersolute approach...
Conventional polarized continuum model calculations of solvatochromic shifts on electronic excitation energies using popular quantum chemical programs (e.g., Gaussian or Turbomole) include the noninertial and inertial bulk-solvent polarization, which will be called electrostatics, but not dispersion interactions specific effects like hydrogen bonding. For n→π* acetone in several solvents, we estimated nonelectrostatic contributions two ways: (i) vertical (VEM) Li et al. (Int. J. Quantum...