Ultrafast reorientation of dangling OH groups at the air-water interface using femtosecond vibrational spectroscopy

We report the real-time measurement of the ultrafast reorientational motion of water molecules at the water-air interface, using femtosecond time- and polarization-resolved vibrational sum-frequency spectroscopy. Vibrational excitation of dangling OH bonds along a specific polarization axis induces a transient anisotropy that decays due to the reorientation of vibrationally excited OH groups. The reorientation of interfacial water is shown to occur on subpicosecond time scales, several times faster than in the bulk, which can be attributed to the lower degree of hydrogen bond coordination at the interface. Molecular dynamics simulations of interfacial water dynamics are in quantitative agreement with experimental observations and show that, unlike in bulk, the interfacial reorientation occurs in a largely diffusive manner.     

Comparison of phase behavior between water soluble and insoluble surfactants at the air-water interface

The surface phase behavior of 2-hydroxyethyl myristate (2-HEM) has been studied in Langmuir monolayers by measuring surface pressure (π)-area (A) isotherms with a film balance and observing monolayer morphology with a Brewster angle microscope (BAM). These results are compared with the phase behavior of 2-hydroxyethyl laurate (2-HEL) in Gibbs monolayers studied by measuring π-time (t) curves and observing monolayer morphology. The π-A isotherms of 2-HEM show a first-order phase transition from a liquid expanded (LE) phase to a liquid condensed (LC) phase in the temperature range between 5 and 35 °C whereas the π-t curves of 2-HEL represent a similar phase transition in the temperature range between 2 and 25 °C. The critical surface pressure, π_c necessary for the phase transitions increases with increasing temperature in both the cases. The LC domains formed in 2-HEM show circular shapes, which are independent of the temperature. In contrast, the circular domains having stripe texture formed at lower temperatures show a shape transition to fingering domains with uniform brightness at 15 °C. The amphiphile, 2-HEM having 13-carbon chain has higher line tension than 2-HEL that has 11-carbon chain as tail. Thus, for 2-HEM, this high line tension always dominates over other factors giving rise to circular domains at the all studied temperatures.     

Study of photooxidation of styrene-butadiene copolymers by surface pressure measurements at the air-water interface

Block and random copolymers of butadiene and styrene as well as polybutadiene and polystyrene homopolymers have been investigated with respect to their monolayer properties and photooxidation behavior. Whereas polystyrene and block copolymers of styrene and butadiene form stable monolayers, polybutadienes and random copolymers do not interact with the aqueous subphase. The monolayer properties of block copolymers with different styrene content indicate that polybutadiene also contributes to the surface pressure. Photo-oxidation of random and block copolymers of styrene and butadiene leads to a significant enhancement in surface pressure of the monolayers due to the generation of groups which can effectively interact with the aqueous surface. FTIR spectral studies show the formation of carbonyl, hydroxyl, and hydroperoxyl groups in the polymers on photooxidation. A comparison of the pressure-area isotherms of random and block copolymers oxidized in solution indicates that there is an energy transfer from butadiene to styrene units in the case of random copolymers, resulting in a protective effect of butadiene units from oxidation. In addition, in the monolayers of oxidized block copolymers, a phase transition occurs which is attributed to the extrusion of polystyrene blocks from the monolayer. The surface pressure-area isotherms and the rates of photooxidation are strongly dependent on the microstructure of polybutadiene as well as on whether oxidation is performed in solution or at the oxygen-water interface.     

Ultrafast vibrational and structural dynamics of the proton in liquid water

The dynamical behavior of excess protons in liquid water is investigated using femtosecond vibrational pump-probe spectroscopy. By resonantly exciting the O-H+-stretching mode of the H9O4(+) (Eigen) hydration structure of the proton and probing the subsequent absorption change over a broad frequency range, the dynamics of the proton is observed in real time. The lifetime of the protonic stretching mode is found to be approximately 120 fs, shorter than for any other vibration in liquid water. We also observe the interconversion between the H9O4(+) (Eigen) and H5O2(+) (Zundel) hydration structures of the proton. This interconversion, which constitutes an essential step of proton transport in water, is found to occur on an extremely fast (< 100 fs) time scale.     

Spontaneous patterning of quantum dots at the air-water interface

Nanoparticles deposited at the air-water interface are observed to form circular domains at low density and stripes at higher density. We interpret these patterns as equilibrium phenomena produced by a competition between an attraction and a longer-ranged repulsion. Computer simulations of a generic pair potential with attractive and repulsive parts of this kind, reproduce both the circular and stripe patterns. Such patterns have a potential use in nanoelectronic applications.     

Relation between bulk compressibility and surface energy of electron-hole liquids

Attention is drawn to the existence of an empirical relation χσ/a_B¹ ～ 1 between the compressibility, the surface energy and the excitonic radius in electron-hole liquids.     

Molecular orientation and surface potential at the liquid water interface

Preliminary results are reported on the molecular orientation and surface potential of liquid water at 4°C.     

Electron-stimulated reactions at the interfaces of amorphous solid water films driven by long-range energy transfer from the bulk

The electron-stimulated production of D2 from amorphous solid D2O deposited on Pt(111) is investigated as a function of film thickness. The D2 yield has two components that have distinct reaction kinetics. Using isotopically layered films of H2O and D2O demonstrates that the D2 is produced in reactions that occur at both the Pt/amorphous solid water (ASW) interface and the ASW/vacuum interface, but not in the bulk. The energy for the reactions, however, is absorbed in the bulk of the films and electronic excitations diffuse to the interfaces where they drive the reactions.     

Ultrafast resonance energy transfer in bio-molecular systems

In this article, we present our consistent efforts to explore thedynamical pathways of the migration of electronic radiation by usingultrafast (picosecond/femtosecond time scales) Förster resonance energytransfer (FRET) technique. The ultrafast non-radiative energy migration froman intrinsic donor fluorophore (Tryptophan, Trp214) present in domain IIA ofa transporter protein human serum albumin (HSA) to variousnon-covalently/covalently attached organic/inorganic chromophores includingphotoporphyrin IX (PPIX), polyoxovanadate[V₁₅As₆O₄₂(H₂O)]^-6clusters (denoted as V₁₅) and CdS quantum dots (QDs) has beenexplored. We have also used other covalently/non-covalently attachedextrinsic fluorogenic donors (NPA, ANS) in order to exploit the dynamics ofresonance energy migration of an enzyme α-chymotrypsin (CHT). Theuse of extrinsic donor instead of intrinsic Trp in CHT avoids ambiguity inthe location of the donor molecule as seven tryptophans are present in theenzyme CHT. We have labeled CHT with ANS (1-anilinonaphthalene-8-sulfonate)and NPA (4-nitrophenyl anthranilate) and studied FRET. Labeling of DNA hasalso been done in the context that the DNA bases have very low quantum yieldfor fluorescence. We have also validated FRET model over nano-surface energytransfer technique (NSET) in the case of quantum clusters and applied thefindings to other QDs. The use of QDs over organic fluorophore was justifiedby least photo-bleaching of QDs compared to organic fluorophore. Our studiesmay find relevance in the exploration of alternate pathway for ultrafastmigration of electronic radiation through FRET to minimize the detrimentaleffect of UV radiation in living organism.     

Efficient non-resonant intermolecular vibrational energy transfer

Molecular excited vibrational states are metastable states and we incorporate their finite lifetimes into the theory of vibrational energy transfer between weakly interacting molecules, i.e., at internuclear distances at which they do not have a chemical bond. Expressions for the effective lifetime of an initially vibrationally excited molecule in the presence of a neighbouring molecule are derived in closed form. These expressions allow one to analyse the physics behind the energy transfer. It is shown that due to different finite lifetimes of the isolated excited molecules, a very efficient vibrational energy transfer can take place between them even if their energies are rather off-resonance. Examples are discussed.     

The temperature dependence of surface second-harmonic generation from the air-water interface

An investigation of the polarization and temperature dependence of surface second-harmonic generation (SHG) at the air-water interface shows that the intensity of the SHG signal decreases over the range 20–70°C. Accounting for the changes in the SHG polarization behaviour with temperature to extract the relative temperature dependence of X_zzz shows that it is similar to that obtained from simulation studies. The role of the interfacial refractive index in the interpretation of the SHG signals is addressed.     

Viscoelastic properties of silica nanoparticle monolayers at the air-water interface

We have investigated the rheological behaviour of silica nanoparticle layers at the air-water interface. Both compressed and deposited layers have been studied in Langmuir troughs and with a bicone rheometer. The compressed layers are more homogeneous and rigid, and the elastic response to continuous, step and oscillatory compression are similar, provided the compression is fast enough and relaxation is prevented. The deposited layers are less rigid and more viscoelastic. Their shear moduli deduced from the oscillatory uniaxial compression are much smaller than those deduced from pure shear deformation suggesting that the effective shear rate is smaller than expected in the compression measurements.     

Examining surface and bulk structures using combined nonlinear vibrational spectroscopies

We combined sum-frequency generation (SFG) vibrational spectroscopy with coherent anti-Stokes Raman scattering (CARS) spectroscopy in one system to examine both surface and bulk structures of materials with the same geometry and without the need to move the sample. Poly(methyl methacrylate) (PMMA) and polystyrene (PS) thin films were tested before and after plasma treatment. The sensitivities of SFG and CARS were tested by varying polymer film thickness and using a lipid monolayer.     

Electrostatic origin of the Frank elastic energy and anisotropic line tension of the domains in monolayers at the air-water interface

The free energy of condensed phase domains in monolayers at the air-water interface has been analyzed by taking into account the surface pressure, line tension, and electrostatic energy due to the normal and in-plane spontaneous polarization. We found that this free energy was reduced to the sum of the Frank elastic energy and anisotropic line tension, which were used to reproduce the shapes of domains in fatty acid monolayers, in the limit of small orientational deformation. Domains in monolayers are interesting systems as a meeting point between the physics of liquid crystals and electrostatics.     

Dynamics at the air-water interface revealed by evanescent wave light scattering

A new tool to study surface phenomena by evanescent wave light scattering is employed for an investigation of an aqueous surface through the water phase. When the angle of incidence passes the critical angle of total internal reflection, a high and narrow scattering peak is observed. It is discussed as an enhancement of scattering at critical angle illumination. Peak width and height are affected by the interfacial profile and the focusing of the beam. In addition, the propagation of capillary waves was studied at the surface of pure water and in the presence of latex particles and amphiphilic diblock copolymers. The range of the scattering vectors where propagating surface waves were detected is by far wider than standard surface quasi-elastic light scattering (SQELS) and comparable with those of X-ray photon correlation spectroscopy (XPCS).     

Molecular dynamics study of the vibrational relaxation of OCl and OCl in the bulk and the surface of water and acetonitrile

The vibrational relaxation of OCl and OCl⁻ in the bulk and the liquid/vapor interface of water and acetonitrile is studied by molecular dynamics computer simulations. Both equilibrium calculations of the vibrational friction and non-equilibrium simulation of the energy relaxation are used to elucidate the factors that influence the rate of energy relaxation in systems that represent polar ionic and non-ionic solutes in polar protic and non-protic solvents. We find that, in agreement with previous experimental and theoretical studies, the relaxation of the ionic solute is much faster than that of the non-ionic solute in both the solvents. However, while the relaxation is slowed down considerably when the non-ionic solute is transferred from the bulk to the interface, no such surface effect is found in the case of the ionic solute. This behavior can be explained by noting that the ionic solute is able to keep its first solvation shell intact upon transfer to the interface and that the main contribution to the friction is due to the Lennard-Jones part of the intermolecular potential.     

On the vibration modes of the air-water interface in the presence of surface films

Summary A numerical method is described which allows one to obtain the solutions of the linearized Navier-Stokes equation for the case of wave motion at the air-water interface in the presence of both soluble and insoluble films. The results are shown, and we discuss evidence of two vibration modes,i.e. transversal and longitudinal waves. Their behaviour appears to be closely linked, especially in the case of insoluble films.

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Riassunto Viene descritto un metodo numerico che permette di ottenere le soluzioni dell'equazione di Navier-Stokes linearizzata nel caso di moto ondoso all'interfaccia aria-acqua in presenza di film solubili ed insolubili. Sono mostrati i risultati e si discute l'evidenza di due modi vibrazionali,i.e. onda longitudinale e trasversale. Il loro comportamento appare strettamente correlato, specialmente nel caso di film insolubili.

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Резюме Описывается численный метод, который позволяет получить решения линеаризованного уравнения Навье-Стокса для случая волнового движения границы раздела воздух-вода при наличии растворимых и нерастворимых пленок. Приводятся результаты, и мы обсуждаем появление двух колебательных мод, т.е. поперечных и продольных волн. Показывается, что их поведение тесно связано, особенно в случае нерастворимых пленок.

     

高激发振动态RbH（Х1Σ+,ν″=15～22）与H2,N2的振动-振动碰撞能量转移

脉冲激光激发Rb原子至6 D态,Rb(6 D)与H2反应生成RbH(Х1Σ+,ν″=0～2)振动态。研究了RbH(Х1Σ+)高位振动态与H2,N2间的碰撞弛豫过程,利用泛频泵浦分别激发Х1Σ+(ν″=0)至Х1Σ+(ν″=15～22)各振动态,检测激光激发Х1Σ+(ν″)至A1Σ+(ν′),测量A1Σ+(ν′)的时间分辨激光感应荧光光谱,利用Stern-Volmer方程,得到振动能级ν″的总的弛豫速率系数kν(H2)。在H2和N2的混合气体中,总弛豫速率系数kν(H2+N2)与α(H2的摩尔配比)成直线的关系,其斜率为kν(H2)-kν(N2),而截距为kν(N2)。对于ν″<18主要发生单量子弛豫(Δν=1)过程,kν(H2)和kν(N2)与振动量子数ν″均成线性增加关系。对于ν″≥18,多量子弛豫(Δν≥2)过程及共振振动-振动转移起重要作用。对于RbH(ν″=21)+N2(0),测量ν″=16的布居数时间演化轮廓,在20μs内有一个锐锋,在100～200μs内有一个较低的宽峰,锐锋相应于RbH(ν″=21)+N2(0)→RbH(ν″=16)+N2(1)的共振转移过程,而宽峰是由相继的单量子过程产生的。