Chemical Reactions and Solvation at Liquid Interfaces:  A Microscopic Perspective

Benjamin, Ilan

doi:10.1021/cr950230+

Cited by 366 publications

(368 citation statements)

References 234 publications

Supporting

Mentioning

348

Contrasting

Unclassified

Order By: Relevance

“…Two interface regions are also evident approximately (12.5 Å from the center of the box, and the vapor phase corresponds to the regions of nearzero density. A hyperbolic tangent function can be fit to the density profile: 35 The width of our interface region is chosen as the "10-90" thickness. 36 This thickness describes the density change from 90 to 10% of the bulk water density.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Hydrogen-Bond Dynamics in the Air−Water Interface

2005

View full text Add to dashboard Cite

Hydrogen-bond (H-bond) dynamics in the air-water interface is studied by molecular dynamics simulations. The analysis reveals that the dynamics of breaking and forming hydrogen bonds in the air-water interface is faster than that in bulk water for the polarizable water models. This is in contrast to the results found on a protein surface. We show that the difference stems from more rapid translational diffusion in the interface. When the effect of pair diffusion is eliminated, the hydrogen-bond dynamics in the interface is observed to be slower than that in the bulk. This occurs because the number of water molecules adjacent to a hydrogenbonded pair and available to accept or donate a hydrogen bond is smaller in the interface than in the bulk. The comparison between polarizable water models and fixed-charge models highlights the potential importance of the polarization effect in the water-vapor interface.

show abstract

Section: Resultsmentioning

confidence: 99%

“…The first is defined by an interaction energy between two water molecules more negative than -10 kJ/mol. 35 The second definition is based on the relative geometry between a pair of water molecules. This definition requires the oxygen-oxygen distance to be less than 3.5 Å and the H-O‚‚‚O angle to be less than 30°.…”

Section: Resultsmentioning

confidence: 99%

Hydrogen-Bond Dynamics in the Air−Water Interface

2005

View full text Add to dashboard Cite

show abstract

“…89 The molecular structure, orientation and dynamics at nonpolar material/water interfaces have been studied by ab initio calculation, MD simulation, or them combined. 5,6,7,8,9,10,11,12,13,90,91 It appears that some different conclusions were drawn on the molecular orientation and structure of the air/water interface in different studies. 6,91,92 Nevertheless, many of these studies concluded that the dipole vector of the interfacial water molecules prefers lying parallel to the interface and have one of the O-H bond protrude out of the liquid phase.…”

Section: Molecular Structure At Air/water Interfacementioning

confidence: 99%

“…12,38,39 Besides SHG and SFG-VS experimental studies, 33,40 Structure and dynamics of water molecules at the air/water interface have also been intensively discussed with theoretical simulations. 5,6,7,8,9,10,11,12,13 Even though with so much efforts and progresses both by experimentalists and theoreticians, our detailed understanding of air/water interface is still limited. Just as indicated by B. C. Garrett recently, 41 '...(direct) experiments are difficult to perform because the liquid interface is disordered, dynamic, and small (typically only a few molecules wide) relative to the bulk'.…”

Section: Introductionmentioning

confidence: 99%

Polarization and experimental configuration analyses of sum frequency generation vibrational spectra, structure, and orientational motion of the air/water interface

Gan¹,

Wu²,

Zhang³

et al. 2006

The Journal of Chemical Physics

249

332

View full text Add to dashboard Cite

Here we report a detailed study on spectroscopy, structure and dynamics of water molecules at air/water interface, investigated with Sum Frequency Generation Vibrational Spectroscopy (SFG-VS). Quantitative polarization and experimental configuration analysis of the SFG data in different polarizations with four sets of experimental configurations can shed new lights on our present understanding of the air/water interface. Firstly, we concluded that the motion of the interfacial water molecules can only be in a limited angular range, instead rapidly varying over a broad angular range in the vibrational relaxation time suggested previously. Secondly, because different vibrational modes of different molecular species at the interface has different symmetry properties, polarization and symmetry analysis of the SFG-VS spectral features can help assignment of the SFG-VS spectra peaks to different interfacial species. These analysis concluded that the narrow 3693cm −1 and broad 3550cm −1 peaks belong to C∞v symmetry, while the broad 3250cm −1 and 3450cm −1 peaks belong to the symmetric stretching modes with C2v symmetry. Thus, the 3693cm −1 peak is assigned to the free OH, the 3550cm −1 peak is assigned to the single hydrogen bonded OH stretching mode, and the 3250cm −1 and 3450cm −1 peaks are assigned to interfacial water molecules as two hydrogen donors for hydrogen bonding (with C2v symmetry), respectively. Thirdly, analysis of the SFG-VS spectra concluded that the singly hydrogen bonded water molecules at the air/water interface have their dipole vector direct almost parallel to the interface, and is with a very narrow orientational distribution. The doubly hydrogen bond donor water molecules have their dipole vector point away from the liquid phase.

show abstract

“…We investigated the difference in adsorption and desorption of liposome-DNA complexes for the inner and the outer biomembrane models. The constitution (%) of the different kinds of phospholipids in the inside and outside biomembrane models used here was (PE, PS, PC, SM, PI) = (40, 18, 33, 6, 3), (9,3,44,31,13), respectively. We obtained liposome-DNA complex by mixing 100 µl PBS buffer solution with 4 µl liposome (Invitrogen, Lipofectamine 2000, diameter: 100 -400 nm) and 100 µl PBS (pH 7.4) buffer solution dissolving 1.6 µg DNA (Invitrogen, plasmid pCMV, SPORT-βgal, 7853 bp.).…”

mentioning

confidence: 99%