Dynamical Discrete/Continuum Linear Response Shells Theory of Solvation: Convergence Test for NH4+ and OH− Ions in Water Solution Using DFT and DFTB Methods

Lima, Guilherme Ferreira de; Duarte, Hélio A.; Pliego, Josefredo R.

doi:10.1021/jp110202e

Cited by 22 publications

(27 citation statements)

References 75 publications

(129 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Thus, it is highly desirable to develop more general theories of hybrid discrete‐continuum solvation. The shells theory of solvation is another hybrid approach . Essentially, the solvent is divided in two shells: S 1 and S 2 .…”

Section: Theorymentioning

confidence: 99%

“…This method is relatively expensive because it involves generation of several configurations followed by single point quantum mechanical calculations. For example, in the study of the solvation of small ions, 500 snapshots were selected for the ensemble average. Despite this high computational cost, it was successfully applied in the study of the hydroxylamine isomerization equilibrium in aqueous solution .…”

Section: Theorymentioning

confidence: 99%

See 1 more Smart Citation

Hybrid discrete‐continuum solvation methods

Pliego

Riveros

2019

WIREs Comput Mol Sci

Self Cite

View full text Add to dashboard Cite

Hybrid discrete‐continuum approaches for solvation have been widely applied for diverse problems in chemistry suck as pKa calculation in aqueous and nonaqueous solvents, activation free energy barriers for ionic processes in solution, and surface reactions. A special version of this approach, the cluster‐continuum quasichemical model, has also been used for establishing a single‐ion solvation free energy scale in different solvents compatible with the tetraphenylarsonium tetraphenylborate assumption. The use of discrete‐continuum solvation methods can lead to meaningful improvement with respect to pure continuum solvation models for modeling diverse chemical process in solution. In the case of pKa calculations, there are cases where the root mean squared error is as large as 7 pKa units with pure continuum solvation model and becomes around 1 pKa unit with the hybrid approach. For complex reactions in solution, errors as large as 10 kcal/mol for activation free energies with the pure continuum approach can be substantially reduced with the inclusion of explicit solvent molecules. A discussion of the theory of hybrid discrete‐continuum methods is also presented and further development is expected in the coming years. This article is categorized under: Structure and Mechanism > Reaction Mechanisms and Catalysis Software > Quantum Chemistry Molecular and Statistical Mechanics > Free Energy Methods

show abstract

Section: Theorymentioning

confidence: 99%

Section: Theorymentioning

confidence: 99%

Hybrid discrete‐continuum solvation methods

Pliego

Riveros

2019

WIREs Comput Mol Sci

Self Cite

View full text Add to dashboard Cite

show abstract

“…Given that a QM treatment of solvent might be desirable, the careful researcher may next wonder how much solvent should be treated quantum mechanically. A number of studies have explored this question for different molecular properties, [61][62][63][64][65][66] and the study of convergence of excitation energies with increasing size of molecular environment has become an area of active research. [10][11][12][67][68][69] Although in some systems a large amount of QM solvent may not be critical for accurately computing the property of interest, we have found that for excited states, values within approximately 0.05 eV of the converged value can be obtained with a full solvation shell treated with QM, as shown in Figure 3.…”

Section: Combining Qm Explicit Solvent With Classical Solvent Modelsmentioning

confidence: 99%

Modeling absorption spectra of molecules in solution

Zuehlsdorff

Isborn

2018

Int J of Quantum Chemistry

View full text Add to dashboard Cite

The presence of solvent tunes many properties of a molecule, such as its ground and excited state geometry, dipole moment, excitation energy, and absorption spectrum. Because the energy of the system will vary depending on the solvent configuration, explicit solute-solvent interactions are key to understanding solution-phase reactivity and spectroscopy, simulating accurate inhomogeneous broadening, and predicting absorption spectra. In this tutorial review, we give an overview of factors to consider when modeling excited states of molecules interacting with explicit solvent. We provide practical guidelines for sampling solute-solvent configurations, choosing a solvent model, performing the excited state electronic structure calculations, and computing spectral lineshapes. We also present our recent results combining the vertical excitation energies computed from an ensemble of solute-solvent configurations with the vibronic spectra obtained from a small number of frozen solvent configurations, resulting in improved simulation of absorption spectra for molecules in solution.excited states, TDDFT, solvation, inhomogeneous broadening, absorption spectra | INTRODUCTIONThe presence of solvent around a molecule affects its energy, properties, dynamics, and reactivity, in both the ground and excited state. Because many excited state phenomena of chemical interest happen in solution and in complex interfacial environments, including photosynthesis, photocatalysis, photoinduced charge and proton transfer, and fluorescence in biological systems, it is important to be able to model these excited state reactions while accurately simulating the solvent environment. In addition, both static and time-resolved absorption and fluorescence spectroscopies serve as useful tools to elucidate chemical reactions and pathways, and simulation of these solution-phase spectra can help to achieve understanding of the electronic rearrangements governing chemical reactions.If theoretical models are to provide reliable simulations of solution-phase chemistry, accurate models of the solvent environment are required.The solvent environment can have a strong influence on an absorption spectrum due to polarization and direct solute-solvent interactions such as hydrogen bonding. Therefore, the modeling of absorption spectra of molecules in solution is often considered a vital step in developing and benchmarking methods to account for the complex solvent environment.Although continuum solvent approaches are computationally attractive because they use the bulk properties of the solvent to polarize a solute, and thus, usually do not sample solute-solvent configurations, in reality it is specific solvent configurations rather than a solvent continuum that determine excited state properties. Also, the simulation of spectral lineshapes, such as those shown in Figure 1 that include both the highenergy tail due to vibronic transitions and the inhomogeneous broadening due to solute-solvent interactions, poses a significant challenge for continuum methods. T...

show abstract

“…The nitrogen atom acts as a base, receiving a proton of the attacking nucleophilic atom, whereas the oxygen atom acts as an acid, forming a hydrogen bond with the carbonyl oxygen and transferring the proton. 8 The most recent study by Lima et al 9 using Shells Theory of Solvation (STS) 10,11 has predicted that the neutral form is 3.5 kcal mol −1 more stable. In the next step, the -NH 3 + group moves to the phenoxide oxygen and induces the breakdown of the tetrahedral intermediate.…”

Section: Introductionmentioning

confidence: 99%

The role of ammonia oxide in the reaction of hydroxylamine with carboxylic esters

2015

Self Cite

View full text Add to dashboard Cite

Theoretical calculations indicate that hydroxylamine can exist in both neutral and zwitterionic (ammonia oxide) forms in aqueous solution, the former being 3.5 kcal mol(-1) more stable. In this report, we have studied the reaction mechanism of hydroxylamine with phenyl acetate and analyzed the role of the zwitterionic isomer. We have observed that the main reaction pathway takes place through the zwitterionic form with a concerted mechanism, not involving the classical tetrahedral intermediate. Attack by the nitrogen atom (via neutral isomer) has a minor contribution and it is also a concerted process. The activation free energy barriers in aqueous solution were calculated at the MP4/TZVPP + diff level for gas phase energies, CPCM for optimization and frequencies, and through single point calculation of the solvation free energy using the SM8 method. Our theoretically predicted barriers are 20.8 and 23.8 kcal mol(-1) for O and N attack, respectively, in very good agreement with the experimental values of 20.4 and 22.3 kcal mol(-1), respectively. Our results support the view that hydroxylamine is a very special nucleophile and the reactivity of this functional group should be further investigated.

show abstract

Dynamical Discrete/Continuum Linear Response Shells Theory of Solvation: Convergence Test for NH₄⁺ and OH⁻ Ions in Water Solution Using DFT and DFTB Methods

Cited by 22 publications

References 75 publications

Hybrid discrete‐continuum solvation methods

Hybrid discrete‐continuum solvation methods

Modeling absorption spectra of molecules in solution

The role of ammonia oxide in the reaction of hydroxylamine with carboxylic esters

Contact Info

Product

Resources

About