On the Reorientation and Hydrogen-Bond Dynamics of Alcohols

Vartia, Anthony A.; Mitchell-Koch, Katie R.; Stirnemann, Guillaume; Laage, Damien; Thompson, Ward H.

doi:10.1021/jp206875k

Cited by 45 publications

(84 citation statements)

References 43 publications

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“…Since these ions vary in both shape and size, effects are expected to be more complex than those arising from excluded volumes alone. 34,44 As observed earlier, 32,43,45 H-bond switching events in these systems have also been found to be associated with a significant amount of translation−rotation coupling.…”

Section: Introductionsupporting

confidence: 70%

Orientational Jumps in (Acetamide + Electrolyte) Deep Eutectics: Anion Dependence

2015

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All-atom molecular dynamics simulations have been carried out to investigate orientation jumps of acetamide molecules in three different ionic deep eutectics made of acetamide (CH3CONH2) and lithium salts of bromide (Br(–)), nitrate (NO3(–)) and perchlorate (ClO4(–)) at approximately 80:20 mole ratio and 303 K. Orientational jumps have been dissected into acetamide–acetamide and acetamide–ion catagories. Simulated jump characteristics register a considerable dependence on the anion identity. For example, large angle jumps are relatively less frequent in the presence of NO3(–) than in the presence of the other two anions. Distribution of jump angles for rotation of acetamide molecules hydrogen bonded (H-bonded) to anions has been found to be bimodal in the presence of Br(–) and is qualitatively different from the other two cases. Estimated energy barrier for orientation jumps of these acetamide molecules (H-bonded to anions) differ by a factor of ∼2 between NO3(–) and ClO4(–), the barrier height for the latter being lower and ∼0.5kBT. Relative radial and angular displacements during jumps describe the sequence ClO(4)– > NO3(–) > Br(–) and follow a reverse viscosity trend. Jump barrier for acetamide–acetamide pairs reflects weak dependence on anion identity and remains closer to the magnitude (∼0.7kBT) found for orientation jumps in molten acetamide. Jump time distributions exhibit a power law dependence of the type, P(tjump) ∝ A(tjump/τ)(−β), with both β and τ showing substantial anion dependence. The latter suggests the presence of dynamic heterogeneity in these systems and supports earlier conclusions from time-resolved fluorescence measurements.

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Section: Introductionsupporting

confidence: 70%

Orientational Jumps in (Acetamide + Electrolyte) Deep Eutectics: Anion Dependence

2015

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“…Alkyl groups restrict the number of configurations amenable to hydrogen bonding, and this effect increases with the number and size of the alkyl groups surrounding O-H moieties. [57][58][59] Molecular dynamics calculations have shown that the percolating hydrogen-bonded network of water persists in H 2 O-MeOH liquid mixtures up to x MeOH ∼ 0.5. 49 Thus, our experimental results are consistent with the involvement of such extended networks in LR-SIE at air-liquid interfaces.…”

Section: Resultsmentioning

confidence: 99%

Long-range specific ion-ion interactions in hydrogen-bonded liquid films

Enami

Colussi

2013

The Journal of Chemical Physics

102

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Anions populate fluid interfaces specifically. Here, we report experiments showing that on hydrogenbonded interfaces anions interact specifically over unexpectedly long distances. The composition of binary electrolyte (Na + , X − /Y − ) films was investigated as a function of solvent, film thickness, and third ion additions in free-standing films produced by blowing up drops with a high-speed gas. These films soon fragment into charged sub-micrometer droplets carrying excess anions detectable in situ by online electrospray ionization mass spectrometry. We found that (1) the larger anions are enriched in the thinner (nanoscopic air-liquid-air) films produced at higher gas velocities in all (water, methanol, 2-propanol, and acetonitrile) tested solvents, (2) third ions (beginning at sub-μM levels) specifically perturb X − /Y − ratios in water and methanol but have no effect in acetonitrile or 2-propanol. Thus, among these polar organic liquids (of similar viscosities but much smaller surface tensions and dielectric permittivities than water) only on methanol do anions interact specifically over long, viz.: r i − r j /nm = 150 (c/μM) −1/3 , distances. Our findings point to the extended hydrogenbond networks of water and methanol as likely conduits for such interactions. © 2013 AIP Publishing LLC. [http://dx

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“…4, we show the reactive time correlation function, 1 − C rp (t), which decays at longer times with a time constant of τ = 1/k = 3.1 ps, which is consistent with previous determinations of the H-bond jump time in water. 21,25 Also shown is the C Hrp (t) ≡ ⟨δH(0) n r (0) n p (t)⟩ TCF that gives the activation energy via Eq. (14).…”

Section: H-bond Exchanges In Watermentioning

confidence: 99%

Removing the barrier to the calculation of activation energies

Mesele

Thompson

2016

The Journal of Chemical Physics

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Approaches for directly calculating the activation energy for a chemical reaction from a simulation at a single temperature are explored with applications to both classical and quantum systems. The activation energy is obtained from a time correlation function that can be evaluated from the same molecular dynamics trajectories or quantum dynamics used to evaluate the rate constant itself and thus requires essentially no extra computational work. Published by AIP Publishing. [http://dx

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On the Reorientation and Hydrogen-Bond Dynamics of Alcohols

Cited by 45 publications

References 43 publications

Orientational Jumps in (Acetamide + Electrolyte) Deep Eutectics: Anion Dependence

Orientational Jumps in (Acetamide + Electrolyte) Deep Eutectics: Anion Dependence

Long-range specific ion-ion interactions in hydrogen-bonded liquid films

Removing the barrier to the calculation of activation energies

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