Nondiffusive Rotational Jump Dynamics in Ethyl Ammonium Nitrate

Dasari, Sathish; Mallik, Bhabani S.

doi:10.1021/acs.jpcb.8b06372

Cited by 9 publications

(15 citation statements)

References 82 publications

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“…8, respectively. In comparison with the hydrogen-bond jump mechanism observed in EAN, 111 the change in both distances during the hydrogen-bond jump in MAF is not systematic. Visual inspection of the jump event displays the hydrogen bond going through an intermediate state in which the N−H of the ammonium group is hydrogenbonded with both the oxygen atoms of the same (mechanism-I) formate anion or different (mechanism-II) formate anions.…”

Section: Resultsmentioning

confidence: 70%

“…The shoulder might arise from the bifurcated hydrogen-bonding networks within MAF, as in earlier reports. 21,96 The C−O RDFs are very much similar in both functionals. The coordination number trend is the same as predicted for earlier cases.…”

Section: Resultsmentioning

confidence: 87%

“…110 Recently, we used the same approach to calculate the rotational jump dynamics of the ammonium group around the C−N bond of ethyl ammonium in ethyl ammonium nitrate (EAN) ionic liquids. 111 In another recent study, we used this approach to calculate the hydrogen-bond jump dynamics in water using different dispersion-corrected BLYP and PBE functionals. 112 Utilizing the same in MAF, we found two different hydrogen-bond jump mechanisms similar to EAN.…”

Section: Resultsmentioning

confidence: 99%

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Cohesiveness and Nondiffusive Rotational Jump Dynamics of Protic Ionic Liquid from Dispersion-Corrected FPMD Simulations

2020

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We have investigated the liquid phase of an ionic liquid (IL), methylammonium formate (MAF), through the first principles molecular dynamics simulations using van der Waals (vdW) corrected exchange and correlation functionals of the density functional theory. The simulations were carried out to obtain a comparative study of various properties of the MAF using two different generalized gradient approximation functionals (Becke− Lee−Yang−Parr (BLYP) and Perdew−Burke−Ernzerhof (PBE)) along with three types of dispersion corrections (D2, D3, and dispersion-corrected atom-centered one-electron potentials), and two values of the plane-wave cutoff (300 and 600 Ry). We have evaluated the effects of various electronic parameters in describing the hydrogen-bonded structure and dynamical properties of MAF by performing 10 sets of molecular dynamics simulations. Thermodynamic properties are found to be sensitive to the details of electronic structure calculations. Our results of PBE functionals with the semiempirical vdW method provide the best agreement with experimental density. The overall density predictions match the cohesive energy trends, and the calculations incorporating dispersion forces exhibit enhanced intermolecular interactions within the hydrogen-bonded IL framework. All of the vdW-corrected BLYP functionals, mainly the dispersion-corrected atom-centered one-electron potential (DCACP) method, illustrate a well-defined structure of liquid MAF. To look into the dynamical perspective of the hydrogen-bond descriptions, we elucidate two possible mechanistic pathways of the hydrogen-bond jump events between the counterions. The hydrogen-bond breaking and forming mechanism along with the collision dynamics can be best described by incorporating dispersion interactions alongside the exchange and correlation functionals within the Kohn−Sham scheme. The rattling dynamics of ions are observed for dispersion-corrected functionals. Hence, an accurate representation of the delicately balanced interactive forces within ionic liquids is a necessary step toward a better description of its thermophysical and structural properties along with the associated ionic dynamics.

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Section: Resultsmentioning

confidence: 70%

Section: Resultsmentioning

confidence: 87%

Section: Resultsmentioning

confidence: 99%

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Cohesiveness and Nondiffusive Rotational Jump Dynamics of Protic Ionic Liquid from Dispersion-Corrected FPMD Simulations

2020

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“…According to the DSE description, a solute should experience the viscous drag of the first solvent shell as it moves through solution. Departures from hydrodynamic behavior can be correlated to many phenomena such as specific solute-solvent interactions (e.g., hydrogen bonding, electrostatic interactions, solvophobic interactions) [31] and "jump" mechanisms [32,33] where a molecule moves in a rapid angular (rotational) manner, but does so with nondiffusive motion, usually on an ultrafast time scale. Solvation in ILs is often probed using a dye molecule to measure spectral shift (absorption or emission) and Stokes shift changes upon solvent reorganization.…”

Section: Introductionmentioning

confidence: 99%

Coumarin 153 Dynamics in Ethylammonium Nitrate: The Effects of Dilution with Methanol

Heitz

Sabo

Robillard

2021

Sustainable Chemistry

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Magic angle intensity decay and dynamic fluorescence anisotropy measurements were made on the binary solvent system composed of ethylammonium nitrate ([N2,0,0,0+][NO3−], EAN) + methanol (MeOH) across the complete EAN mole fraction range (xIL = 0–1) using the neutral dipolar solute coumarin 153 (C153) at 295 K. Stokes–Einstein–Debye (SED) hydrodynamic theory was used as a model framework to assess the C153 rotational reorientation dynamics. Departure from stick SED prediction was observed (in contrast to literature reports that used cationic or anionic dyes) and indicated a significant influence of domain nanoheterogeneity on probe dynamics. Steady-state spectroscopy indicated minimal changes in spectral peak and width with mole fraction, except at xIL = 0.3 where absorption widths decreased by ~170 cm−1, signaling that C153 sensed a change in solution heterogeneity. Magic angle intensity decays corroborated the steady-state observation and the excited-state lifetimes showed a marked change from xIL = 0.2–0.4 where EAN-EAN interactions became notably more significant. C153 average rotation times (⟨τrot⟩) showed significant solvent decoupling with increased EAN. The rotational data were fit to a power law dependence, ⟨τrot⟩ ∝ (ηT)p, where p = 0.82, demonstrating the presence of dynamic heterogeneity in the EAN/MeOH solutions. With increased EAN, rotation times showed that the heterogeneity became increasingly more significant since the rotation times systematically decreased away from the hydrodynamic stick limit.

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“…See, for example, Refs. (Das and Paul, 2017;Chand et al, 2018;Dasari and Mallik, 2018;Kaur and Kashyap, 2018;Awasthi et al, 2016;Awasthi and Nair, 2017;Awasthi et al, 2018;Chugh and Ranganathan, 2016;Ghosh and Ranganathan, 2017;Chugh and Ranganathan, 2017;Sarkar et al, 2019;Maity and Reddy, 2018;Nandi et al, 2017;Hridya and Mukherjee, 2018;Sharma and Ghorai, 2018;Ahalawat and Murarka, 2017;Rout and Srinivasan, 2018;Shekar and Swathi, 2018;Kumawat and Chakrabarty, 2017;Palchowdhury and Bhargava, 2018;Mandal et al, 2018;Ahalawat and Mondal, 2018;Hasnain and Bandyopadhyay, 2015;Dutta and Nandi, 2015) for representative work from these groups in recent years. Also, many institutes now have multiple research groups working in statistical mechanics and computer simulations.…”

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confidence: 99%

Statistical Mechanics in Theoretical Chemistry in India : Past, present and a bit of future

Chandra¹,

Bagchi²

2019

PINSA

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While the subject of statistical mechanics is intensely active in physics departments across India, with considerable activity even in mathematics departments, the same cannot be said for average chemistry departments in India where statistical mechanics is relatively less taught and even less pursued. This is to be contrasted with USA and many other developed countries (Germany, Israel) where statistical mechanics and spectroscopy are major disciplines in the physical chemistry departments. The situation, however, has changed rapidly in the past few decades. In this article we discuss the developments in this important area in the recent past, with emphasis both on analytical approach and those based on computer simulations. We also attempt to look into future problems where our efforts could be directed fruitfully.

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Nondiffusive Rotational Jump Dynamics in Ethyl Ammonium Nitrate

Cited by 9 publications

References 82 publications

Cohesiveness and Nondiffusive Rotational Jump Dynamics of Protic Ionic Liquid from Dispersion-Corrected FPMD Simulations

Cohesiveness and Nondiffusive Rotational Jump Dynamics of Protic Ionic Liquid from Dispersion-Corrected FPMD Simulations

Coumarin 153 Dynamics in Ethylammonium Nitrate: The Effects of Dilution with Methanol

Statistical Mechanics in Theoretical Chemistry in India : Past, present and a bit of future

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