Development of force fields for binary systems: Application to a dimethylsulfoxide (DMSO) – Oxygen mixture

Belletti, Gustavo Daniel; Schulte, Erica; Colombo, Estefanía; Schmickler, Wolfgang; Quaino, Paola

doi:10.1016/j.cplett.2019.136778

Cited by 7 publications

(9 citation statements)

References 30 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…To this end, a significant increase in computer power in the last two decades has permitted us to resort to accurate quantum mechanical (QM) methods, able to yield reliable reference data, over which specific FFs can be parameterized. Exploiting this possibility, several automated or semi-automated methods have been proposed that are able to deliver such quantum mechanically derived force fields (QMD-FFs). ,− Although all of these procedures are rooted in the possibility of deriving FF parameters based on selected QM data, they present different features, according to which they may be classified. One possible criterion is to consider the type of FF parameters employed: most of the aforementioned QMD-FF procedures concern either with the description of the single-molecule flexibility (intramolecular or valence FFs), ,,,,,,,,,, with the interaction between two or more species (intermolecular or noncovalent FFs), ,,,,,,,,,, or with both these aspects simultaneously. ,,,,,,,− , Alternatively, the different QMD-FFs can be also classified based on the complexity of their defining model functions.…”

Section: Introductionmentioning

confidence: 99%

“…Exploiting this possibility, several automated or semi-automated methods have been proposed that are able to deliver such quantum mechanically derived force fields (QMD-FFs). ,− Although all of these procedures are rooted in the possibility of deriving FF parameters based on selected QM data, they present different features, according to which they may be classified. One possible criterion is to consider the type of FF parameters employed: most of the aforementioned QMD-FF procedures concern either with the description of the single-molecule flexibility (intramolecular or valence FFs), ,,,,,,,,,, with the interaction between two or more species (intermolecular or noncovalent FFs), ,,,,,,,,,, or with both these aspects simultaneously. ,,,,,,,− , Alternatively, the different QMD-FFs can be also classified based on the complexity of their defining model functions. Indeed, exploiting the wealth of information contained in the parent QM description, more complex and physically motivated models can be adopted in the FF definition, allowing, for instance, to separately account for three-body terms, polarization effects, dispersion interactions, etc. ,,,,,,, …”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Automated Parameterization of Quantum Mechanically Derived Force Fields for Soft Materials and Complex Fluids: Development and Validation

Vilhena

Silveira

Livotto

et al. 2021

J. Chem. Theory Comput.

View full text Add to dashboard Cite

The reliability of molecular dynamics (MD) simulations in predicting macroscopic properties of complex fluids and soft materials, such as liquid crystals, colloidal suspensions, or polymers, relies on the accuracy of the adopted force field (FF). We present an automated protocol to derive specific and accurate FFs, fully based on ab initio quantum mechanical (QM) data. The integration of the JOYCE and PICKY procedures, recently proposed by our group to provide an accurate description of simple liquids, is here extended to larger molecules, capable of exhibiting more complex fluid phases. While the standard JOYCE protocol is employed to parameterize the intramolecular FF term, a new automated procedure is here proposed to handle the computational cost of the QM calculations required for the parameterization of the intermolecular FF term. The latter is thus obtained by integrating the old PICKY procedure with a fragmentation reconstruction method (FRM) that allows for a reliable, yet computationally feasible sampling of the intermolecular energy surface at the QM level. The whole FF parameterization protocol is tested on a benchmark liquid crystal, and the performances of the resulting quantum mechanically derived (QMD) FF were compared with those delivered by a general-purpose, transferable one, and by the third, "hybrid" FF, where only the bonded terms were refined against QM data. Lengthy atomistic MD simulations are carried out with each FF on extended 5CB systems in both isotropic and nematic phases, eventually validating the proposed protocol by comparing the resulting macroscopic properties with other computational models and with experiments. The QMD-FF yields the best performances, reproducing both phases in the correct range of temperatures and well describing their structure, dynamics, and thermodynamic properties, thus providing a clear protocol that may be explored to predict such properties on other complex fluids or soft materials.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Automated Parameterization of Quantum Mechanically Derived Force Fields for Soft Materials and Complex Fluids: Development and Validation

Vilhena

Silveira

Livotto

et al. 2021

J. Chem. Theory Comput.

View full text Add to dashboard Cite

show abstract

“…This might introduce a further obstacle, which can be overcome by refining or fully re-parameterizing the FF, based on accurate Quantum Mechanical (QM) data, as recently reported by several groups. [44][45][46][47][48][49] Once the reliability of the classical MD trajectories has been validated, a very convenient method to compute spectra of complex and flexible systems in explicit environments is performing a Classical Ensemble Average of Vertical Excitations (CEA-VE). It essentially consists in performing a sufficiently long and accurate MD trajectory, from which a number of uncorrelated snapshots, large enough to ensure convergence, is extracted, and successively computing vertical transition energies and intensities for each frame.…”

mentioning

confidence: 99%

Accounting for Vibronic Features through a Mixed Quantum-Classical Scheme: Structure, Dynamics, and Absorption Spectra of a Perylene Diimide Dye in Solution

Segalina

Cerezo

Prampolini

et al. 2020

J. Chem. Theory Comput.

View full text Add to dashboard Cite

The optical absorption spectrum of a perylene diimide (PDI) dye in acetonitrile solution is simulated using the recently developed (J. Chem. Theory Comput. 2020, 16, 1215–1231) Ad-MD|gVH method. This mixed quantum-classical (MQC) approach is based on an adiabatic (Ad) separation of soft(classical)/stiff(quantum) nuclear degrees of freedom and expresses the spectrum as a conformational average (over the soft coordinates) of vibronic spectra (for the stiff coordinates) obtained through the generalized vertical Hessian (gVH) vibronic approach. The average is performed over snapshots extracted from classical molecular dynamics (MD) runs, performed with a specifically parameterized quantum-mechanically derived force field (QMD-FF). A comprehensive assessment of the reliability of different approaches, designed to reproduce spectral shapes of flexible molecules, is here presented. First, the differences in the sampled configurational space and their consequences on the prediction of the absorption spectra are evaluated by comparing the results obtained by means of the specific QMD-FF and of a general-purpose transferable FF with those of a reference ab initio MD (AIMD) in the gas phase, in both a purely classical scheme (ensemble average) and in the Ad-MD|gVH framework. Next, classical ensemble average and MQC predictions are also obtained for the PDI dynamics in solution and compared with the results of a ″static″ approach, based on vibronic calculations carried out on a single optimized perylene diimide structure. In the classical ensemble average approach, the remarkably different samplings obtained with the two FFs lead to sizeable changes in both position and intensity of the predicted spectra, with the one computed along the QMD-FF trajectory closely matching its AIMD counterpart. Conversely, at the Ad-MD|gVH level of theory, the different samplings deliver very similar vibronic spectra, indicating that the error found in the absorption spectra obtained with the general-purpose FF mainly concerns the stiff modes. In fact, it can be effectively corrected by the quadratic extrapolation performed by gVH to locate the minima of the ground- and excited-state potential energy surfaces along such coordinates. Furthermore, in the perspective of studying the self-assembling process of PDI dyes and the vibronic spectra of large-size aggregates, the use of a molecule-specific QMD-FF also appears mandatory, considering the significant errors found in the GAFF trajectory in the flexible lateral chain populations, which dictate the supramolecular aggregation properties.

show abstract

“…From the point of view of the FFs, it can be foreseen that for accurate applications, besides the introduction of polarizable FFs to account for the mutual solute-solvent polarization already mentioned, general purpose FFs will be replaced by QMD-FFs, optimized both for the solute-solvent interactions, and also for the intramolecular motion of the solute and specific for each of its electronic states. [226][227][228][229] QMD-FFs offer the possibility to replace a QM/MM trajectory with a much faster fully MM/MM trajectory, and have been proven to be helpful to investigate solvation problems. 43 They should be particularly suited when extended sampling before photoexcitation is required, or when many initial conditions and/or long excited-state propagations are needed.…”

Section: Discussionmentioning

confidence: 99%

Quantum and semiclassical dynamical studies of nonadiabatic processes in solution: achievements and perspectives

Santoro

Green

Martínez‐Fernández

et al. 2021

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

show abstract

Development of force fields for binary systems: Application to a dimethylsulfoxide (DMSO) – Oxygen mixture

Cited by 7 publications

References 30 publications

Automated Parameterization of Quantum Mechanically Derived Force Fields for Soft Materials and Complex Fluids: Development and Validation

Automated Parameterization of Quantum Mechanically Derived Force Fields for Soft Materials and Complex Fluids: Development and Validation

Accounting for Vibronic Features through a Mixed Quantum-Classical Scheme: Structure, Dynamics, and Absorption Spectra of a Perylene Diimide Dye in Solution

Quantum and semiclassical dynamical studies of nonadiabatic processes in solution: achievements and perspectives

Contact Info

Product

Resources

About