Hydrogen Bond Dynamics of Methyl Acetate in Methanol

Pagliai, Marco; Muniz‐Miranda, Francesco; Cardini, Gianni; Righini, Roberto; Schettino, Vincenzo

doi:10.1021/jz1010994

Cited by 39 publications

(51 citation statements)

References 20 publications

(45 reference statements)

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“…However, for MA the slope of the straight line, which is proportional to μ 2 , increases with the number of H-bonds. As indicated (Table 1), the trend is in qualitative agreement with a previous theoretical study, 34 which showed that upon H-bond formation the transition dipole moment of the C=O stretching vibration of MA is increased. 39 For EA, the transition dipole moments were found to be similar for the 0hb and 1hb species, whereas formation of two H-bonds slightly decreases the transition dipole moment (see Table 1).…”

Section: Resultssupporting

confidence: 91%

“…33 Their results indicate that H-bond formation with the solvent can lead to a significant decrease in the vibrational lifetime of this mode, which is in agreement with the current study. In addition, Righini and coworkers 34 have used ab initio molecular dynamics simulations to show that such H-bonds have a lifetime of 0.5 to 2 ps. Here, we expand the scope of these previous studies by further characterizing the chemical exchange kinetics between differently H-bonded states of MA and EA molecules in methanol under equilibrium conditions.…”

Section: Introductionmentioning

confidence: 99%

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Kinetics of Exchange between Zero-, One-, and Two-Hydrogen-Bonded States of Methyl and Ethyl Acetate in Methanol

Chuntonov

Pazos

et al. 2015

J. Phys. Chem. B

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It has recently been shown that the ester carbonyl stretching vibration can be used as a sensitive probe of local electrostatic field in molecular systems. To further characterize this vibrational probe and extend its potential applications, we studied the kinetics of chemical exchange between differently hydrogen-bonded (H-bonded) ester carbonyl groups of methyl acetate (MA) and ethyl acetate (EA) in methanol. We found that while both MA and EA can form zero, one, or two H-bonds with the solvent, the population of the 2hb state in MA is significantly smaller than that in EA. Using a combination of linear and non-linear infrared measurements and numerical simulations, we further determined the rate constants for the exchange between these differently H-bonded states. We found that for MA the chemical exchange reaction between the two dominant states (i.e., 0hb and 1hb states) has a relaxation rate constant of 0.14 ps−1, whereas for EA the three-state chemical exchange reaction occurs in a predominantly sequential manner with the following relaxation rate constants: 0.11 ps−1 for exchange between 0hb and 1hb states, 0.12 ps−1 for exchange between 1hb and 2hb states.

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Section: Resultssupporting

confidence: 91%

Section: Introductionmentioning

confidence: 99%

Kinetics of Exchange between Zero-, One-, and Two-Hydrogen-Bonded States of Methyl and Ethyl Acetate in Methanol

Chuntonov

Pazos

et al. 2015

J. Phys. Chem. B

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“…The algorithm adopted to compute wavelet transform W n ( s ) in the Fourier space is expressed as 22 where ω k is the angular frequency for the k th normal mode and F̂ k and ψ̂ are the Fourier transformations of the time series F n and the mother wavelet ψ( t ), respectively. The mother wavelet ψ( t ) is represented aswhere the parameters ω 0 and σ are set as reported elsewhere.…”

Section: Theoretical Calculationsmentioning

confidence: 99%

Physics behind the Barrier to Internal Rotation of an Acetyl Chloride Molecule: A Combined Approach from Density Functional Theory, Car–Parrinello Molecular Dynamics, and Time-Resolved Wavelet Transform Theory

Dutta¹,

Bhattacharjee

Chowdhury

2018

ACS Omega

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The physics behind the barriers to internal rotation of acetyl chloride (AC) molecule has been reported. The AC molecule closely resembles the molecular structure of acetaldehyde; the only subtle difference is the presence of a heavy chlorine atom in place of the hydrogen atom of the aldehyde group for the latter. This paper aims to study the effect of substitution of the heavy chlorine atom on the barrier energetics of the AC molecule. The reason behind the barrier for the AC molecule has been estimated for the first time from the unified approach using barrier energetics, natural bond orbital, nuclear virial, and relaxation analyses using density functional theory, Car–Parrinello molecular dynamics, and wavelet transform theory. Complete analyses reveal the concomitant relaxations of both the in-plane C methyl –C 1 and C methyl –H 4 bonds toward understanding the origin of the barrier due to internal rotation for the AC molecule. The large negative value of “ V 6 ” further suggests that both the abovementioned degrees of freedom are coupled with the −CH 3 torsional vibration of the molecule. The coupling matrix ( H 12 ) element has also been estimated. Time-resolved band stretching frequencies of C methyl –C 1 and C 1 –Cl 3 bonds of the AC molecule, as obtained from wavelet transformation analysis, primarily preclude the possibility of coupling between the C 1 –Cl 3 bond and the torsional motion associated with the methyl group of the molecule.

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“…On the other hand, MD simulation provides one of the most direct ways to theoretically investigate the molecular behavior [29], which is not accessible to experimental approaches in complex systems, such as a system involving H-bond interactions [30]. Furthermore, in order to obtain useful insight into the H-bond dynamics, it is important to establish the correlation between the simulation results of structural or vibrational properties and experimental measurement results [31].…”

Section: Introductionmentioning

confidence: 99%

Molecular insights into the damping mechanism of poly(vinyl acetate)/hindered phenol hybrids by a combination of experiment and molecular dynamics simulation

Zhang

et al. 2015

RSC Adv.

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The fundamental mechanism of the improved damping properties of poly(vinyl acetate) (PVAc) contributed by the introduction of hindered phenol was systematically elucidated by two-dimensional infrared (2D IR) spectroscopy, dynamic mechanical analysis (DMA), differential scanning calorimeter (DSC), X-ray diffraction (XRD) and molecular dynamics (MD) simulation. 2D IR results revealed the hydrogen bonds (H-bonds) evolution from intermolecular H-bonds to H-bonds network of PVAc/hindered phenol. Subsequent DMA results revealed that the damping properties of PVAc exhibited two different degrees of the improvement due to the addition of hindered phenol. Meanwhile, DSC results showed that all hybrids were miscible as concentration fluctuations change irregularly. According to the XRD observation of only amorphous hindered phenol existing in PVAc matrix, further MD simulation,based on an amorphous cell, characterized the number of H-bonds, the binding energy and the fractional free volume (FFV) of the hybrids. It was observed that the variation tendency of the simulation data was in accordance with the experimental results. * Therefore, the damping mechanism of PVAc/hindered phenol hybrids was proposed through a detailed analysis on the synergy effects of the number of intermolecular H-bonds and binding energy between PVAc and hindered phenol as well as the FFV or dynamic heterogeneity.

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Hydrogen Bond Dynamics of Methyl Acetate in Methanol

Cited by 39 publications

References 20 publications

Kinetics of Exchange between Zero-, One-, and Two-Hydrogen-Bonded States of Methyl and Ethyl Acetate in Methanol

Kinetics of Exchange between Zero-, One-, and Two-Hydrogen-Bonded States of Methyl and Ethyl Acetate in Methanol

Physics behind the Barrier to Internal Rotation of an Acetyl Chloride Molecule: A Combined Approach from Density Functional Theory, Car–Parrinello Molecular Dynamics, and Time-Resolved Wavelet Transform Theory

Molecular insights into the damping mechanism of poly(vinyl acetate)/hindered phenol hybrids by a combination of experiment and molecular dynamics simulation

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