Isotropic Brillouin spectra of liquids having an internal degree of freedom

Isotropic Brillouin spectra of the two chemically similar van der Waals glass forming liquids, 1,1(')-di(4-methoxy-5-methylphenyl)cyclohexane (BMMPC) and 1,1(')-bis(p-methoxy-phenyl)cyclohexane (BMPC) and ortho-terphenyl (OTP), were studied in a broad temperature and pressure range in order to characterize the effect of internal relaxations on the damping of longitudinal phonons. Such relaxations are present in BMPC, while in BMMPC and OTP they are strongly hindered. The authors show that in BMPC (with strong internal relaxations) the damping (broadening) of longitudinal phonons (Brillouin peaks) is much stronger than in BMMPC and OTP (with weaker internal relaxations). The contributions of the internal and structural relaxations to the phonon damping can be separated using high pressure, due to their very different pressure dependences. They show that internal relaxations strongly contribute to the damping of longitudinal phonons at all temperatures and should be taken into account in theoretical models describing the Brillouin spectra of supercooled liquids.     

Brillouin scattering study of gelatin gel

Brillouin spectra as functions of temperature for gelatin-water systems of various concentrations are reported. These new results are discussed in light of the model from Marqusee and Deutch. We found this model to be a reasonably good theory for Brillouin scattering from gels. The sound speed in a network and the frictional damping have been evaluated.     

Lattice dynamics of tetrahedrally bonded boron nitride probed by inelastic X-ray scattering

We report experimental results on the lattice dynamics of zincblende and wurtzite boron nitride obtained by inelastic X-ray scattering (IXS) on polycrystalline samples. The generalized vibrational density of states and the orientation averaged longitudinal acoustic phonon dispersion are determined, and the longitudinal and shear sound speeds as well as the Debye temperature are derived. Our results are compared to ab initio lattice dynamics calculations and available elastic and thermodynamic data.     

The effect of intramolecular relaxations on the damping of longitudinal and transverse phonons in polysiloxanes studied by Brillouin spectroscopy

The effect of intramolecular relaxations on the damping of longitudinal and transverse phonons was studied in poly(methylphenylsiloxane) (PMPS) and poly(ethylmethylsiloxane) (PEMS) polymers by means of Brillouin spectroscopy. It is shown that studies of the polarized and depolarized Brillouin spectra as functions of temperature and pressure allow for the separation of the contributions of the internal and structural relaxations to the damping of longitudinal and transverse phonons, respectively. In polymers with intramolecular relaxations these processes contribute not only to the damping of longitudinal phonons, according to theoretical predictions, but also transverse phonons, in contradiction to the theory.     

Phonon vibrational frequencies of all single-wall carbon nanotubes at the lambda point: reduced matrix calculations

With a simple method-the reduced matrix method, we simplified the calculation of the phonon vibrational frequencies according to SWNTs structure and their phonon symmetric property and got the dispersion properties of all SWNTs at Gamma point in Brillouin zone, whose diameters lie between 0.6 and 2.5 nm. The calculating time is shrunk about 2-4 orders. A series of the dependent relationships between the diameters of SWNTs and the frequencies of Raman and IR active modes are given. Several fine structures including "glazed tile" structures in omega approximately d figures are found, which might predict a certain macro-quantum phenomenon of the phonons in SWNTs.     

Phonons in suspensions of hard sphere colloids: volume fraction dependence

The propagation of sound waves in suspensions of hard sphere colloids is studied as a function of their volume fraction up to random close packing using Brillouin light scattering. The rich experimental phonon spectra of up to five phonon modes are successfully described by theoretical calculations based on the multiple scattering method. Two main types of phonon modes are revealed: Type A modes are acoustic excitations which set up deformations in both the solid (particles) and the liquid (solvent) phases; for type B modes the stress and strain are predominantly localized near the interface between the solid particles and the surrounding liquid (interface waves). While the former become harder (increase their effective sound velocity) as the particle volume fraction increases the latter become softer (the corresponding sound velocity decreases).     

The liquidlike ordering of lipid A-diphosphate colloidal crystals: the influence of Ca2+, Mg2+, Na+, and K+ on the ordering of colloidal suspensions of lipid A-diphosphate in aqueous solutions

A comprehensive study was performed on electrostatically stabilized aqueous dispersion of lipid A-diphosphate in the presence of bound Ca2+, Mg2+, K+, and Na+ ions at low ionic strength (0.10-10.0-mM NaCl, 25 degrees C) over a range of volume fraction of 1.0 x 10(-4)< or =phi< or =4.95 x 10(-4). These suspensions were characterized by light scattering (LS), quasielastic light scattering, small-angle x-ray scattering, transmission electron microscopy, scanning electron microscopy, conductivity measurements, and acid-base titrations. LS and electron microscopy yielded similar values for particle sizes, particle size distributions, and polydispersity. The measured static structure factor, S(Q), of lipid A-diphosphate was seen to be heavily dependent on the nature and concentration of the counterions, e.g., Ca2+ at 5.0 nM, Mg2+ at 15.0 microM, and K+ at 100.0 microM (25 degrees C). The magnitude and position of the S(Q) peaks depend not only on the divalent ion concentration (Ca2+ and Mg2+) but also on the order of addition of the counterions to the lipid A-diphosphate suspension in the presence of 0.1-microM NaCl. Significant changes in the rms radii of gyration (R2G) 1/2 of the lipid A-diphosphate particles were observed in the presence of Ca2+ (24.8+/-0.8 nm), Mg2+ (28.5+/-0.7 nm), and K+ (25.2+/-0.6 nm), whereas the Na+ salt (29.1+/-0.8 nm) has a value similar to the one found for the de-ionized lipid A-diphosphate suspensions (29.2+/-0.8 nm). Effective particle charges were determined by fits of the integral equation calculations of the polydisperse static structure factor, S(Q), to the light-scattering data and they were found to be in the range of Z*=700-750 for the lipid A-diphosphate salts under investigation. The light-scattering data indicated that only a small fraction of the ionizable surface sites (phosphate) of the lipid A-diphosphate was partly dissociated (approximately 30%). It was also discovered that a given amount of Ca2+ (1.0-5.0 nM) or K+ (100 microM) influenced the structure much more than Na+ (0.1-10.0-mM NaCl) or Mg2+ (50 microM). By comparing the heights and positions of the structure factor peaks S(Q) for lipid A-diphosphate-Na+ and lipid A-diphosphate-Ca2+, it was concluded that the structure factor does not depend simply on ionic strength but more importantly on the internal structural arrangements of the lipid A-diphosphate assembly in the presence of the bound cations. The liquidlike interactions revealed a considerable degree of ordering in solution accounting for the primary S(Q) peak and also the secondary minimum at large particle separation. The ordering of lipid A-diphosphate-Ca2+ colloidal crystals in suspension showed six to seven discrete diffraction peaks and revealed a face-centered-cubic (fcc) lattice type (a=56.3 nm) at a volume fraction of 3.2 x 10(-4)< or =phi< or =3.9 x 10(-4). The K+ salt also exhibited a fcc lattice (a=55.92 nm) at the same volume fractions, but reveals a different peak intensity distribution, as seen for the lipid A-diphosphate-Ca2+ salt. However, the Mg2+ and the Na+ salts of lipid A-diphosphate showed body-centered-cubic (bcc) lattices with a=45.50 nm and a=41.50 nm, respectively (3.2 x 10(-4)< or =phi< or =3.9 x 10(-4)), displaying the same intensity distribution with the exception of the (220) diffraction peaks, which differ in intensity for both salts of lipid A-diphosphate.     

Single mode phonon energy transmission in functionalized carbon nanotubes

Although the carbon nanotube (CNT) features superior thermal properties in its pristine form, the chemical functionalization often required for many applications of CNT inevitably degrades the structural integrity and affects the transport of energy carriers. In this article, the effect of the side wall functionalization on the phonon energy transmission along the symmetry axis of CNT is studied using the phonon wave packet method. Three different functional groups are studied: methyl (-CH(3)), vinyl (-C(2)H(3)), and carboxyl (-COOH). We find that, near Γ point of the Brillouin zone, acoustic phonons show ideal transmission, while the transmission of the optical phonons is strongly suppressed. A positive correlation between the energy transmission coefficient and the phonon group velocity is observed for both acoustic and optical phonon modes. On comparing the transmission due to functional groups with equivalent point mass defects on CNT, we find that the chemistry of the functional group, rather than its molecular mass, has a dominant role in determining phonon scattering, hence the transmission, at the defect sites.     

Collective dynamics in molten potassium: an inelastic x-ray scattering study

The high-frequency collective dynamics of molten potassium has been investigated by inelastic x-ray scattering, disclosing an energy/momentum transfer region unreachable by previous inelastic neutron scattering (INS) experiments. We find that a two-step relaxation scenario, similar to that found in other liquid metals, applies to liquid potassium. In particular, we show how the sound velocity determined by INS experiments, exceeding the hydrodynamic value by approximately 30%, is the higher limit of a speedup, located in the momentum region 1 < Q < 3 nm(-1), which marks the departure from the isothermal value. We point out how this phenomenology is the consequence of a microscopic relaxation process that, in turn, can be traced back to the presence of "instantaneous" disorder, rather than to the crossover from a liquid to solidlike response.     

Temperature-dependent Raman scattering of silicon nanowires

Silicon nanowires with narrowly distributed diameters of 20-30 nm have been fabricated by chemical vapor deposition on an anodized aluminum oxide (AAO) substrate. The first-order and second-order Raman scatterings of the silicon nanowires have been studied in a temperature range from 123 to 633 K. Both of the first-order and second-order Raman peaks were found to shift and broaden with increasing temperature. The experimental results were analyzed by combining the phonon confinement effect, anharmonic phonon processes and lattice stress effect. It was found that the intensities of the first-order and second-order Raman bands have different dependences on temperature. The value of relative intensities I(2TA)int/I(2TO)int for silicon nanowires was found to be larger than that of bulk silicon, and increase with rising measurement temperature. We ascribe this phenomenon to the participation of phonons with a large wave vector value of Raman scattering caused by both the phonon confinement effect and the temperature effect.     

Relaxations of thermosets. VIII. Brillouin light scattering during the curing of diglycidyl ether of bisphenol-A thermosets

The kinetics of sol-gel-glass transformations have been studied in the thermosets of diglycidyl ether of bisphenol A cured with diamino diphenyl methane and diamino diphenyl sulfone, at different temperatures using Brillouin light scattering. The Shape of the Brillouin peak is generally broad. This is attributed to the damping of elastic waves in the mixture of unpolymerized low-molecular weight fluid and the polymer chains forming the networks. The Brillouin peak becomes sharp and narrow at complete curing of the thermosets. The phonon velocity increases and the attenuation decreases with the curing time. These changes occur in two steps with the second step appearing near the gelling time of the thermosets. A semilogarithmic plot of the time for the velocity and attenuation to reach half of their total change against the reciprocal temperature yields a straight line with different slopes for the two thermosets. It is suggested that Brillouin light scattering is a useful non-destructive, in-line, method for control in the processing of epoxy thermosets.     

Spectroscopic characterization of ambers and amber-like materials

Longitudinal acoustic (LA) phonon of Baltic, Dominican and Kuji ambers, amber-like rosin and synthetic acrylic resin has been investigated by means of Brillouin light scattering (BLS) at room temperature. We observed a pair of LA phonon peaks and a broad quasi-elastic scattering peak in backscattering spectra from ambers. The LA phonon frequencies were found to be 16.97–17.11 GHz for Baltic ambers, 17.23–17.68 GHz for Dominican ambers and 17.70–17.97 GHz for Kuji ambers, respectively. We would like to point out that the LA phonon frequency can be a good physical quantity to specify the amber-producing district. We also present a correlation between the BLS spectrum and infrared absorption spectrum of ambers and amber-like materials.     

Collective dynamics of hydrated β-lactoglobulin by inelastic x-ray scattering

Inelastic x-ray scattering measurements of hydrated β-lactoglobulin (β-lg) were performed to investigate the collective dynamics of hydration water and hydrated protein on a picosecond time scale. Samples with different hydration levels h [=mass of water (g)/mass of protein (g)] of 0 (dry), 0.5, and 1.0 were measured at ambient temperature. The observed dynamical structure factor S(Q,ω)/S(Q) was analyzed by a model composed of a Lorentzian for the central peak and a damped harmonic oscillator (DHO) for the side peak. The dispersion relation between the excitation energy in the DHO model and the momentum transfer Q was obtained for the hydrated β-lg at both hydration levels, but no DHO excitation was found for the dry β-lg. The high-frequency sound velocity was similar to that previously observed in pure water. The ratio of the high-frequency sound velocity of hydrated β-lg to the adiabatic one of hydrated lysozyme (h=0.41) was estimated as ～1.6 for h=0.5. The value is significantly smaller than that (～2) of pure water that has the tetrahedral network structure. The present finding thus suggests that the tetrahedral network structure of water around the β-lg is partially disrupted by the perturbation from protein surface. These results are consistent with those reported from Brillouin neutron spectroscopy and molecular dynamics simulation studies of hydrated ribonuclease A.     

Contributions from radiation damping and surface scattering to the linewidth of the longitudinal plasmon band of gold nanorods: a single particle study

The scattering spectra of single gold nanorods with aspect ratios between 2 and 4 have been examined by dark field microscopy. The results show that the longitudinal plasmon resonance (electron oscillation along the long axis of the rod) broadens as the width of the rods decreases from 14 to 8 nm. This is attributed to electron surface scattering. Analysis of the data using gamma = gamma(bulk) + Anu(F)/L(eff), where L(eff) is the effective path length of the electrons and nu(F) is the Fermi velocity, allows us to determine a value for the surface scattering parameter of A = 0.3. Larger rods with widths of 19 and 30 nm were also examined. These samples also show spectral broadening, which is attributed to radiation damping. The relative strengths of the surface scattering and radiation damping effects are in excellent agreement with recent work on spherical gold nanoparticles by S?nnichsen et al., Phys. Rev. Lett., 2002, 88, 077402; and by Berciaud et al., Nano Lett., 2005, 5, 515.     

Longitudinal excitations in Mg-Al-O refractory oxide melts studied by inelastic x-ray scattering

The dynamic structure factor S(Q,omega) of the refractory oxide melts MgAl2O4 and MgAl4O7 is studied by inelastic x-ray scattering with aerodynamic levitation and laser heating. This technique allows the authors to measure simultaneously the elastic response and transport properties of melts under extreme temperatures. Over the wave vector Q range of 1-8 nm-1 the data can be fitted with a generalized hydrodynamic model that incorporates a slow component described by a single relaxation time and an effectively instantaneous fast component. Their study provides estimates of high-frequency sound velocities and viscosities of the Mg-Al-O melts. In contrast to liquid metals, the dispersion of the high-frequency sound mode is found to be linear, and the generalized viscosity to be Q independent. Both experiment and simulation show a weak viscosity maximum around the MgAl4O7 composition.     

Line widths of the 3800 Å singlet transitions in crystalline anthracene

The theory of resonance coupling of Frenkel excitons and phonons is extended to two molecules per unit cell. Intra- and inter-band scattering for the two Davydov components can thus be dealt with on the same footing. Restrictions to nearest neighbour interactions have been removed. Application to anthracene shows that the contribution of librational phonons to the scattering is approximately one hundred times larger than that of translational phonons. The widths of the anthracene components are shown to fit the calculated coupling and known phonon frequencies satisfactorily.     

Relationship between phonon damping and pure dephasing of localized electronic excitations

Effects of quadratic electron—phonon interaction on the zero-phonon line shape of impurity-ion electronic transitions in crystals and on the spectrum of lattice phonons are investigated. Both subsystems (impurity ion and phonons) are treated on an equal fooling, employing the method of double-time thermal Green functions in the random-phase approximation. It is shown that in the case of weak dephasing due to destructive interference effects, a relationship can be established between the pure-dephasing rate of the electronic excitation and the temperature-dependent part of the electron—phonon-limited phonon damping. The phonon linewidth is shown to decrease to a lesser extent than the electronic linewidth when interference effects become enhanced, thus providing information on the dynamical broadening processes even if the electronic pure-dephasing width is too small to be observed.     

Brillouin scattering and rotation translation coupling of (KCN)xX1−x mixed crystals

Brillouin scattering is used to study the concentration and temperature dependence of longitudinal and transverse phonon frequencies of KCN_χBr_1?χ, KCN_χC1_1?χ, and KCN_0.85I_0.15 mixed crystals. Unlike pure KCN, mixed crystals with χ < 0.7 show no phase transition upon cooling, and the transverse acoustic frequency ω_TA(110) displays a minimum at some characteristic temperature T_i.T_i is below the phase transition of pure KCN and depends on the C1^? concentration. The Brillouin data are discussed in terms of coupling of the acoustic phonons with orientational motion of CN^? ions and mean field theory.     

Damping and modification of the multiquanta Davydov-like solitons in molecular chains.

Relaxation of the multivibron soliton in molecular chain on lattice vibrations is investigated within the simple microscopic model. It was shown that its dynamics is governed by the nonlinear Schr?dinger equation containing damping term. Its appearance is the consequence of the emission and absorption of real phonons arising when soliton velocity approaches the phase speed of sound. Explicit time dependence of the soliton parameters results as a consequence of these perturbations. In particular, soliton amplitude decreases while its width increases.     

Raman scattering and efficient UV photoluminescence from well-aligned ZnO nanowires epitaxially grown on GaN buffer layer

Optical phonon confinement and efficient UV emission of ZnO nanowires were investigated in use of resonant Raman scattering (RRS) and photoluminescence (PL). The high-quality ZnO nanowires with diameters of 80-100 nm and lengths of several micrometers were epitaxially grown through a simple low-pressure vapor-phase deposition method at temperature 550 degrees C on the precoated GaN(0001) buffer layer. The increasing intensity ratio of n-order longitudinal optical (LO) phonon (A(1)(nLO)/E(1)(nLO)) with increasing scattering order in RRS reveals the phonon quantum confinement as shrinking the diameter of ZnO nanowires. The exciton-related recombination near the band-edge transition dominate the UV emissions at room temperature as well as at low temperature that exhibits almost no other nonstoichiometric defects in the ZnO nanowires.