A Study of Finite Size Effects and Periodic Boundary Conditions to Simulations of a Novel Theoretical Self‐Consistent Mean‐Field Approach

Yang, Guanda; Nilsson, Fritjof; Schubert, Dirk W.

doi:10.1002/mats.201900023

Cited by 5 publications

(2 citation statements)

References 51 publications

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“…The last 50 ps trajectory of the NVE simulation run was utilized to determine the stretch frequency distribution of the vibrational probes, the average hydrogen-bond lifetimes, rotational anisotropy dynamics, and vibrational spectral diffusion dynamics. We note that smaller boxes are likely associated with finite-size effects and spurious correlation of ions. − Also, the simulations suffer from finite time effects . The finite-size and time effects collectively may introduce systematic errors in the present IL simulations with different density functionals.…”

Section: Computational Methodologymentioning

confidence: 91%

Dynamics of Ionic Liquid through Intrinsic Vibrational Probes Using the Dispersion-Corrected DFT Functionals

Biswas

Mallik

2021

J. Phys. Chem. B

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First principles molecular dynamics simulations have been utilized to study the spectral properties of the protic ionic liquid, methylammonium formate (MAF). All simulations were performed using density functional theory (DFT) and various van der Waals-corrected exchange–correlation functionals. We calculated the vibrational stretch frequency distributions, determined the time–frequency correlations of the intrinsic vibrational probes, the N–H and C–O modes in MAF, and the frequency–structure correlations. We also estimated the average hydrogen-bond lifetimes and orientation dynamics to capture the ultrafast spectral response. The spectroscopic signature of the N–H stretching vibrations using the Becke–Lee–Yang–Parr (BLYP) and Perdew–Burke–Ernzerhof (PBE) functionals displays a spectral shift in the lower frequency side, suggesting stronger hydrogen-bonding interactions represented by the gradient approximation functionals than the van der Waals (vdW)-corrected simulations. The carboxylate frequency profiles with the dispersion-corrected representations are almost similar without a significant difference in the normalized distributions. Besides, the COO stretching frequencies at the peak maxima positions of the PBE functionals exhibit a lesser deviation from the experimental data. Spectral diffusion dynamics of the intrinsic vibrational probes on the cationic and anionic sites of the ionic liquid proceed through a short time relaxation of the intact hydrogen bonds followed by an intermediate time constant and a longer time decay indicating the switchover of hydrogen bonds. Dispersion-corrected atom-centered one-electron potential (DCACP) correction added to the BLYP system slows down the picosecond time scales of frequency correlation and the time constants of rotational motion, lengthening the overall system dynamics. The observed trends in the time-dependent decays of frequency fluctuations and the orientation autocorrelation functions correlate with the structural interactions in liquid MAF and hydrogen-bond dynamics. In this study, we examine the predictions made by different density functional treatments comparing the results of the uncorrected BLYP and PBE representations with the semiempirical vdW methods of Grimme and matching our calculated data with the experimental observations.

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Section: Computational Methodologymentioning

confidence: 91%

Dynamics of Ionic Liquid through Intrinsic Vibrational Probes Using the Dispersion-Corrected DFT Functionals

Biswas

Mallik

2021

J. Phys. Chem. B

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“…The trajectories generated using PBE and dispersion-corrected PBE-D2 functionals were utilized to calculate various properties. Though a box of 13.8 Å might seem too small, finite-size effects and spurious ionic correlations − might often limit the simulations, introducing systematic errors leading to discrepancies. Our computational setup provides a realistic picture.…”

Section: Computational Methodologymentioning

confidence: 99%

Ionic Dynamics and Vibrational Spectral Diffusion of a Protic Alkylammonium Ionic Salt through Intrinsic Cationic N–H Vibrational Probe from FPMD Simulations

Biswas

Mallik

2022

J. Phys. Chem. A

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We employed density functional theory (DFT)-based molecular dynamics simulations to explore the structure, dynamics, and spectral properties of the protic ionic entity trimethylammonium chloride (TMACl). Structural investigations include calculating the site–site radial distribution functions (RDFs), the distribution of constituent cations and anions in three-dimensional space, and combined distribution functions of the hydrogen-bonded pair RDF versus angle, revealing the structural characteristics of the ionic solvation and the intermolecular interactions within ions. Further, we determined the instantaneous vibrational stretching frequencies of the intrinsic N–H stretch probe modes by applying the time-series wavelet method. The associated ionic dynamics within the protic ionic compound were investigated by calculating the time-evolution of the fluctuating frequencies and the frequency-time correlation functions (FFCFs). The time scale related to the local structural relaxation process and the average hydrogen bond lifetime, ion cage dynamics, and mean squared displacement were investigated. The faster decay component of the FFCFs, depicting the intermolecular motion of intact hydrogen bonds in TMACl, is 0.07 ps for the Perdew-Burke-Ernzerhof (PBE)-based simulation and 0.06 ps for the PBE-D2 representation. The slower time scale of the longer picosecond decay time component of PBE and PBE-D2 representations are 3.13 and 2.87 ps, respectively. These picosecond time scales represent more significant fluctuations of the hydrogen-bonding partners in the ionic entity and hydrogen-bond jump events accompanied by large angular jumps. The longest picosecond time scales represent structural relaxation, including large angular jumps and ion-pair dynamics. Also, ion cage lifetimes correlate with the slowest time scale of the associated dynamics of vibrational spectral diffusion despite the type of DFT functional. This study benchmarks DFT treatments of the exchange-correlation functional with and without the van der Waals (vdW) dispersion correction scheme. The inclusion of vdW interactions to the PBE functional represents a less structured state of the ionic entity and faster dynamics of the molecular motions relative to the one predicted by the PBE system. All the results illustrate the necessity of accurately describing the Coulomb interactions, vdW dispersive interactive forces, and localized hydrogen bonds required to sustain the energetic balance in this ionic salt.

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Determining electrical percolation threshold of randomly distributed conductor materials in polymer composites via pathfinding algorithms

Bozyel

Gökcen

2022

Composites Science and Technology

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A Study of Finite Size Effects and Periodic Boundary Conditions to Simulations of a Novel Theoretical Self‐Consistent Mean‐Field Approach

Cited by 5 publications

References 51 publications

Dynamics of Ionic Liquid through Intrinsic Vibrational Probes Using the Dispersion-Corrected DFT Functionals

Dynamics of Ionic Liquid through Intrinsic Vibrational Probes Using the Dispersion-Corrected DFT Functionals

Ionic Dynamics and Vibrational Spectral Diffusion of a Protic Alkylammonium Ionic Salt through Intrinsic Cationic N–H Vibrational Probe from FPMD Simulations

Determining electrical percolation threshold of randomly distributed conductor materials in polymer composites via pathfinding algorithms

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