A State-Specific PCM–DFT method to include dynamic solvent effects in the calculation of ionization energies: Application to DNA bases

Muñoz-Losa, Aurora; Markovitsi, Dimitra; Improta, Roberto

doi:10.1016/j.cplett.2015.05.045

Cited by 17 publications

(24 citation statements)

References 46 publications

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“…If the reaction is largely controlled by static effects, the solvent's relaxation is fast compared to the activation process and the activated complex is largely in thermal equilibrium with the solvent. However, this equilibrium assumption is usually not valid for a chemical reaction in a strongly dipolar and/or slow‐relaxing solvent . In this situation, rate constants will depend on solvent dynamics and will vary with parameters that include density, internal pressure, or viscosity.…”

Section: Definition Of Solvent Effectssupporting

confidence: 58%

“…However,t his equilibrium assumption is usually not valid for ac hemical reactioni nastrongly dipolar and/or slow-relaxing solvent. [141][142][143][144][145][146][147][148] In this situation, rate constants will depend on solventd ynamics and will vary with parameters that include density,i nternal pressure, or viscosity.E speciallyf or rapid chemicalr eactions, the slow relaxation of the solvent will affect the activation process. In such cases, the activation process can be limited by the time taken by molecules to reorient themselves around the transition state.…”

Section: Definition Of Solvent Effectsmentioning

confidence: 99%

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Organic Solvent Effects in Biomass Conversion Reactions

2015

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Transforming lignocellulosic biomass into fuels and chemicals has been intensely studied in recent years. A large amount of work has been dedicated to finding suitable solvent systems, which can improve the transformation of biomass into value‐added chemicals. These efforts have been undertaken based on numerous research results that have shown that organic solvents can improve both conversion and selectivity of biomass to platform molecules. We present an overview of these organic solvent effects, which are harnessed in biomass conversion processes, including conversion of biomass to sugars, conversion of sugars to furanic compounds, and production of lignin monomers. A special emphasis is placed on comparing the solvent effects on conversion and product selectivity in water with those in organic solvents while discussing the origins of the differences that arise. We have categorized results as benefiting from two major types of effects: solvent effects on solubility of biomass components including cellulose and lignin and solvent effects on chemical thermodynamics including those affecting reactants, intermediates, products, and/or catalysts. Finally, the challenges of using organic solvents in industrial processes are discussed from the perspective of solvent cost, solvent stability, and solvent safety. We suggest that a holistic view of solvent effects, the mechanistic elucidation of these effects, and the careful consideration of the challenges associated with solvent use could assist researchers in choosing and designing improved solvent systems for targeted biomass conversion processes.

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Section: Definition Of Solvent Effectssupporting

confidence: 58%

Section: Definition Of Solvent Effectsmentioning

confidence: 99%

Organic Solvent Effects in Biomass Conversion Reactions

2015

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“…These models were frequently used for interpreting liquid PES experiments. The results for neutral solutes were satisfactory (within a typical range 0.1–0.3 eV) providing that the non‐equilibrium character of solvation is acknowledged . The dielectric continuum models, however, fail for multiply charged solutes where the error can amount to 1–2 eV …”

Section: Introductionmentioning

confidence: 89%

“…As a result, we observed the gradual convergence of VIE to the experimental value. We should note at this point that a concept of non‐equilibrium solvation needs to be applied for a proper description of the ionization process . The solvent response can be decomposed into a fast component (corresponding to the electronic polarization) and slow component (corresponding to the nuclear polarization).…”

Section: Methodsmentioning

confidence: 99%

“…The results for neutral solutes were satisfactory (within a typical range 0.1-0.3 eV) providing that the non-equilibrium character of solvation is acknowledged. [8,23,29] The dielectric continuum models, however, fail for multiply charged solutes where the error can amount to 1-2 eV. [14] Here, we apply large-scale cluster-continuum models in which the explicitly solvated solute is further embedded in the dielectric continuum.…”

Section: Introductionmentioning

confidence: 99%

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Efficient modeling of liquid phase photoemission spectra and reorganization energies: Difficult case of multiply charged anions

2017

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An efficient approach for quantitative modeling of liquid phase photoelectron spectra, reorganization energies, and redox potentials with DFT-based molecular dynamics simulations is presented. The method is based on a large scale cluster-continuum approach combined with the so-called reflection principle (RP). Finite size clusters of solute molecules with solvating water molecules are at first generated using either classical molecular dynamics or molecular dynamics with a quantum thermostat which accounts for nuclear quantum effects. In the next step, the electron binding energies are calculated. Finite-size corrections for (i) positions of electron binding energies and (ii) width of the spectrum are evaluated via a dielectric continuum approach. The performance of such a reflection principle with additional broadening approach (RP-AB) for oxidation of multiply charged iron anions, [Fe(CN) ] and [Fe(CN) ] is demonstrated. The role of nuclear quantum effects is discussed as well as the relation between spectroscopic data and electrochemical quantities. Results are compared with recent liquid photoemission experiments, explaining the obstacles for applying liquid phase photoemission spectroscopy as a direct method for obtaining absolute redox potentials and suggesting a way to overcome them. © 2017 Wiley Periodicals, Inc.

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Dielectric continuum methods for quantum chemistry

Herbert

2021

WIREs Comput Mol Sci

136

195

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This review describes the theory and implementation of implicit solvation models based on continuum electrostatics. Within quantum chemistry this formalism is sometimes synonymous with the polarizable continuum model, a particular boundary‐element approach to the problem defined by the Poisson or Poisson–Boltzmann equation, but that moniker belies the diversity of available methods. This work reviews the current state‐of‐the art, with emphasis on theory and methods rather than applications. The basics of continuum electrostatics are described, including the nonequilibrium polarization response upon excitation or ionization of the solute. Nonelectrostatic interactions, which must be included in the model in order to obtain accurate solvation energies, are also described. Numerical techniques for implementing the equations are discussed, including linear‐scaling algorithms that can be used in classical or mixed quantum/classical biomolecular electrostatics calculations. Anisotropic models that can describe interfacial solvation are briefly described. This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods Molecular and Statistical Mechanics > Free Energy Methods

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A State-Specific PCM–DFT method to include dynamic solvent effects in the calculation of ionization energies: Application to DNA bases

Cited by 17 publications

References 46 publications

Organic Solvent Effects in Biomass Conversion Reactions

Organic Solvent Effects in Biomass Conversion Reactions

Efficient modeling of liquid phase photoemission spectra and reorganization energies: Difficult case of multiply charged anions

Dielectric continuum methods for quantum chemistry

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