Solvation energies of ions with ensemble cluster-continuum approach

Lukáš, Tomaník,; Muchová, Eva; Slavı́ček, Petr

doi:10.1039/d0cp02768e

Cited by 35 publications

(36 citation statements)

References 79 publications

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“…Despite important findings were obtained with the hybrid approach of solvation, [56][57][58]64,[67][68][69][70][71][72][73] the results were shown to be considerably affected by the choice of: a) initial state of the solvent (separate molecules or clusters); 60,61,66 b) dielectric continuum model; 61,66 c) electronic structure theory method. 62 In this work using the cluster/continuum framework, we systematically assess the influence of factors a) -c) on resulting solvation free energies of lithium cation in a number of protic (water, methanol) and aprotic (acetonitrile, DMSO, dimethylacetamide, dimethoxyethane, dimethylformamide, gamma-butyrolactone, pyridine, sulfolane) solvents.…”

Section: Introductionmentioning

confidence: 92%

“…The other research groups report similar deviations between the values derived from these cycles. 60,61,66 The origin of the difference between the solvation Gibbs free energies obtained from the "monomer" and "cluster" cycles is to be discussed in the next section.…”

Section: Solvation Gibbs Free Energies From the Clustercontinuum Approachmentioning

confidence: 99%

“…[56][57][58][59] Finally, the performance of implicit solvation models can be further improved (albeit at substantially higher computational costs) via using the so-called hybrid approach that is often referred to as cluster-continuum quasichemical theory or mixed cluster/continuum model and detailed elsewhere. 11,56,[60][61][62][63][64][65][66] At first, the model introduces a few explicit solvent molecules around the solute, forming a cluster and mimicking the solutesolvent specific interactions. At second, the whole cluster is immersed into a dielectric continuum to imitate the non-specific solute-solvent interactions.…”

Section: Introductionmentioning

confidence: 99%

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Ambiguities in solvation free energies from cluster-continuum quasichemical theory: lithium cation in protic and aprotic solvents

Itkis

Cavallo

Yashina

et al. 2021

Phys. Chem. Chem. Phys.

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Section: Introductionmentioning

confidence: 92%

Section: Solvation Gibbs Free Energies From the Clustercontinuum Approachmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Ambiguities in solvation free energies from cluster-continuum quasichemical theory: lithium cation in protic and aprotic solvents

Itkis

Cavallo

Yashina

et al. 2021

Phys. Chem. Chem. Phys.

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“…Density functional theory (DFT) (see Computational Details) with the M06-2X functional and the 6-31++G(d,p) basis set accurately describes the vertical IP (VIP) and adiabatic IP and adiabatic EA (AIP and AEA, respectively) magnitudes in these types of molecules, as validated by benchmark calculations on the thymine nucleobase using complete-active-space second-order perturbation theory (CASPT2) results as a reference [ 20 , 21 ]. The vertical magnitude in solution can be improved by strategies such as those defined by Slavicek, et al beyond polarizable continuum model (PCM) [ 22 , 23 ]. Nevertheless, the important magnitudes here are the adiabatic ones.…”

Section: Resultsmentioning

confidence: 99%

Theoretical Study on the Photo-Oxidation and Photoreduction of an Azetidine Derivative as a Model of DNA Repair

et al. 2021

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Photocycloreversion plays a central role in the study of the repair of DNA lesions, reverting them into the original pyrimidine nucleobases. Particularly, among the proposed mechanisms for the repair of DNA (6-4) photoproducts by photolyases, it has been suggested that it takes place through an intermediate characterized by a four-membered heterocyclic oxetane or azetidine ring, whose opening requires the reduction of the fused nucleobases. The specific role of this electron transfer step and its impact on the ring opening energetics remain to be understood. These processes are studied herein by means of quantum-chemical calculations on the two azetidine stereoisomers obtained from photocycloaddition between 6-azauracil and cyclohexene. First, we analyze the efficiency of the electron-transfer processes by computing the redox properties of the azetidine isomers as well as those of a series of aromatic photosensitizers acting as photoreductants and photo-oxidants. We find certain stereodifferentiation favoring oxidation of the cis-isomer, in agreement with previous experimental data. Second, we determine the reaction profiles of the ring-opening mechanism of the cationic, neutral, and anionic systems and assess their feasibility based on their energy barrier heights and the stability of the reactants and products. Results show that oxidation largely decreases the ring-opening energy barrier for both stereoisomers, even though the process is forecast as too slow to be competitive. Conversely, one-electron reduction dramatically facilitates the ring opening of the azetidine heterocycle. Considering the overall quantum-chemistry findings, N,N-dimethylaniline is proposed as an efficient photosensitizer to trigger the photoinduced cycloreversion of the DNA lesion model.

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“…Semicontinuum or "cluster-continuum" approaches of this kind are common, especially for calculating hydration energies of ions. 8,301,324,331,341,342 An important special case is pK a calculations, 8,[343][344][345][346][347][348][349][350] corresponding to the ionization reaction…”

Section: Herbertmentioning

confidence: 99%

Dielectric continuum methods for quantum chemistry

Herbert

2021

WIREs Comput Mol Sci

142

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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Solvation energies of ions with ensemble cluster-continuum approach

Abstract: An alternative cluster-continuum approach for the calculation of solvation free energies of ions.

Cited by 35 publications

References 79 publications

Ambiguities in solvation free energies from cluster-continuum quasichemical theory: lithium cation in protic and aprotic solvents

Ambiguities in solvation free energies from cluster-continuum quasichemical theory: lithium cation in protic and aprotic solvents

Theoretical Study on the Photo-Oxidation and Photoreduction of an Azetidine Derivative as a Model of DNA Repair

Dielectric continuum methods for quantum chemistry

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