Raman Spectral Density Research Articles

Analyzing the Signal of the Ultrafast Optical Kerr Effect by Considering the Correlation between the Rotational Responses of Molecules in a Liquid

The signal of the ultrafast optical Kerr effect (OKE) in liquids, including toluene C7H8, nitrobenzene C6H5NO2, and acetonitrile C2H3N is analyzed. It is shown that considering the correlation between the orientational and librational responses allows us to determine the rise time of the orientational response associated with the inertial nature of molecular rotations over a time interval of 300–500 fs after the impact of a laser pulse, and to increase the accuracy of determining the form of the Raman spectral density function.

Low-Frequency Molecular Responses in a Liquid upon Recording the Ultrafast Optical Kerr Effect

Low-frequency molecular rotations recorded in a region of 0–150 cm–1 with a high “signal/noise” ratio in the ultrafast optical Kerr effect (OKE), which is a third-order nonlinear optical response upon nonresonant excitation of a liquid by femtosecond laser pulses, are analyzed in detail. It is shown that the reduced Raman spectral density (RSD) derived from experimental data using the well-known deconvolution procedure is ambiguous due to the problem of separating the orientational and librational contributions to the total OKE signal. This fact significantly limits the reliability of information derived about molecular motions in a liquid. For the example of an ultrafast OKE in benzonitrile, it is shown that, in the range of 0–300 fs, rotational responses cannot be considered independent, and the application of a number of additional criteria resulting from the assumption of their correlation allows this ambiguity in deriving the RSD function from experimental data to be removed.

Низкочастотные молекулярные отклики в жидкости при регистрации сверхбыстрого оптического эффекта Керра

AbstractLow-frequency molecular rotations recorded in a region of 0–150 cm^–1 with a high “signal/noise” ratio in the ultrafast optical Kerr effect (OKE), which is a third-order nonlinear optical response upon nonresonant excitation of a liquid by femtosecond laser pulses, are analyzed in detail. It is shown that the reduced Raman spectral density (RSD) derived from experimental data using the well-known deconvolution procedure is ambiguous due to the problem of separating the orientational and librational contributions to the total OKE signal. This fact significantly limits the reliability of information derived about molecular motions in a liquid. For the example of an ultrafast OKE in benzonitrile, it is shown that, in the range of 0–300 fs, rotational responses cannot be considered independent, and the application of a number of additional criteria resulting from the assumption of their correlation allows this ambiguity in deriving the RSD function from experimental data to be removed.

Hydrated Excess Proton Raman Spectral Densities Probed in Floating Water Bridges

Excess proton structures in water remain unclear. The motion and nature of excess protons in water were probed using a supported water bridge structure in electric field (E) with an intensity of ∼106 V/m. The experimental setup generated protons that exhibit a long lifetime. The effect of excess protons in water induced a ∼3% variation in the pH for a 300 V overvoltage at the cathode. The current versus voltage curves show a current space-charge-limited operation. By measuring the space-charge distribution in both the cathode and anode and by adjusting the Mott–Gurney law to the measured excess hydrated proton current and the voltage drop in the cationic space-charge region, the protonic mobility was determined to be ∼200 × 10–8 m2/(V·s) (E ≈ 4 × 106 V/m). This measured mobility, which is typically five times larger than the reported mobility for protons in water, is in agreement with the mechanism outlined by Grotthuss in 1805. The measured mid-Raman spectrum covering 1000–3800 cm–1 range indicates the species character. The hydrated excess proton spectral response through the mid-Raman at 1760 and 3200 cm–1 was attributed to the Zundel complex and the region at ∼2000 to ∼2600 cm–1 response is attributed to the Eigen complex, indicating a core structure simultaneously with a Eigen-like and Zundel-like character, suggesting a rapid fluctuation between these two structures or a new specie.

Aqueous solvation of amphiphilic solutes: concentration and temperature dependent study of the ultrafast polarisability relaxation dynamics

An understanding of the influence of hydrophilic and hydrophobic interactions on the dynamics of solvating water molecules is important in a diverse range of phenomena. The polarisability anisotropy relaxation dynamics of aqueous solutions of the amphiphiles TBA (t-butyl alcohol) and TMAO (trimethylamine N-oxide) have been measured as a function of concentration and temperature. TMAO is shown to have a greater effect on the picosecond relaxation dynamics of water than TBA. This result is consistent with hydrophilic interactions being mainly responsible for the slowing down the polarisability relaxation in aqueous solutions. The room temperature Raman spectral densities of the two solutions are remarkably similar to that of bulk water, an effect which is tentatively ascribed to the formation of nanoscale structure in the solutions, allowing the formation of bulk-like water pools. The temperature dependent spectral density of TMAO remains similar to that of bulk water at all temperatures, while that for TBA shows a marked decrease in the amplitude of the response usually ascribed to a water-water stretch with increasing temperature. This is discussed in terms of the temperature dependent structure of TBA aggregates in solution.

Low-frequency modes of the benzoic acid dimer in chloroform observed by the optical Kerr effect

The low frequency Raman spectral density associated with the intermolecular hydrogen-bonding interaction of benzoic acid in chloroform was investigated through the ultrafast optically-heterodyne-detected optical Kerr effect. The low-frequency solute Raman spectrum was obtained by Fourier transform analysis and subtraction of the solvent spectrum from the solution spectrum. The resulting difference spectrum has a broad band below 150 cm(-1) with a peak at around 80 cm(-1). Previous studies of aromatic liquids suggest that the origin of such a low-frequency band is librational motion, although intermolecular hydrogen-bonding modes in benzoic acid may also contribute. To clarify these contributions to the low-frequency band, methyl benzoate was used to estimate the librational component; its structure is similar to benzoic acid, but it forms no intermolecular hydrogen bonds. Both librational and intermolecular modes were found to contribute to the low-frequency Raman spectrum of the dimer and thus can be separated. These experimental results were compared with the results of density functional theory calculations. In addition, the effect of deuteration on the Raman spectrum was also investigated.

THz Spectra and Dynamics of Aqueous Solutions Studied by the Ultrafast Optical Kerr Effect

The nature and extent of the effects that hydrophilic and hydrophobic solutes have on the dynamics of water molecules continues to be an area of intense experimental and theoretical investigation. In this work, we use the ultrafast optical Kerr effect to measure the picosecond dynamics and THz Raman spectral densities of a series of aqueous solutions. The solutes studied are the hydrophilic urea and formamide and the hydrophobic trimethylamine N-oxide and tetramethylurea. Measurements are made as a function of concentration between <0.1 M and >4 M. At low concentrations (<0.5 M), the THz spectrum resembles that of bulk water, but the picosecond relaxation time, reflecting dynamics in the water H-bonded network, is increased relative to bulk water for all four solutes. The extent to which water relaxation is slowed down depends on the nature of the solute, and is more pronounced for hydrophilic than for hydrophobic solutes. At concentrations above 1 M, a range of solute-solvent and solute-solute interactions gives rise to diverse solute dependent changes in the THz spectral density and to a further slowing down of the picosecond relaxation. The hydrophobic trimethylamine N-oxide has remarkably little effect on the spectral density of water, which may indicate solute self-association and the formation of water pools in more concentrated solutions. For hydrophilic urea and formamide, the THz spectral density suggests that water structure is disrupted at concentrations where most water molecules are part of a solvation shell. At such high concentrations, modes associated with the H-bonded solute make a significant contribution to the spectral density at around 100 cm(-1). The hydrophobic tetramethylurea solute makes a substantial contribution to the spectral density, complicating the interpretation, but a line shape analysis suggests that it also does not strongly perturb the water structure.

Low-Frequency Modes of Aqueous Alkali Halide Solutions: An Ultrafast Optical Kerr Effect Study

A detailed picture of aqueous solvation of ions is central to the understanding of diverse phenomena in chemistry and biology. In this work, we report polarization resolved THz time domain measurements of the Raman spectral density of a wide range of aqueous salt solutions. In particular, the isotropic Raman spectral density reveals the frequency of the hydrogen bond formed between the halide ion and water. The frequency of this mode is measured for the series Cl(-), Br(-), and I(-) as a function of concentration, cation size, and charge. The frequencies extrapolated to zero concentration permit an estimation of the force constant of the mode, which is found to decrease with increasing halide mass and to be similar to the force constant associated with the water-water hydrogen bond. This result is consistent with recent calculations. The extrapolation of the frequency of the chloride hydrogen bond to zero concentration reveals a dependence of the frequency on the nature of the cation. This is ascribed to an interaction between the solvated anion and cation even at the lowest concentration studied here (<0.15 M). It is suggested that this behavior reflects the influence of the electric field of the cation on the hydrogen bond of an adjacent anion. Such interactions should be taken into account when modeling experimental data recorded at concentrations of ions in excess of 0.1 M. These measurements of the isotropic Raman spectral density are compared with those for the anisotropic response, which reflects the frequencies of the full range of hydrogen bonds in aqueous salt solutions. The anisotropic spectral density recovered can be modeled in terms of a concentration-dependent population of water-water H-bonds with a frequency unaffected by the ions, the halide-water hydrogen bonds, and a low-frequency collision-induced contribution.

Low-frequency isotropic and anisotropic Raman spectra of aromatic liquids

The Raman spectra below 300 wavenumbers of six different aromatic molecular liquids have been measured with a time and polarization resolved optical Kerr effect technique. The isotropic and anisotropic contributions were determined to yield the complete third order response, and thus a more detailed description of the microscopic liquid dynamics. The anisotropic contributions accurately reproduced previously published results. Both the isotropic and anisotropic Raman spectral densities shift toward lower frequencies with decreasing molecular weights. The first moment of the isotropic spectral densities scales linearly with the inverse square root of the molecular weight, which is consistent with interaction-induced dynamics in these liquids being driven mainly by motions with a translational character. Also, the isotropic spectral densities could be fit to a single Bucaro-Litovitz function. The exponent delta of this function increases monotonically with the inverse square root of the molecular weight. A possible physical origin of this behavior is discussed.

Zircon M257 ‐ a Homogeneous Natural Reference Material for the Ion Microprobe U‐Pb Analysis of Zircon

We introduce and propose zircon M257 as a future reference material for the determination of zircon U‐Pb ages by means of secondary ion mass spectrometry. This light brownish, flawless, cut gemstone specimen from Sri Lanka weighed 5.14 g (25.7 carats). Zircon M257 has TIMS‐determined, mean isotopic ratios (2s uncertainties) of 0.09100 ± 0.00003 for 206pb/238U and 0.7392 ± 0.0003 for 207pb/235U. Its 206pb/238U age is 561.3 ± 0.3 Ma (unweighted mean, uncertainty quoted at the 95% confidence level); the U‐Pb system is concordant within uncertainty of decay constants. Zircon M257 contains ∼ 840 μg g−1 U (Th/U ∼ 0.27). The material exhibits remarkably low heterogeneity, with a virtual absence of any internal textures even in cathodoluminescence images. The uniform, moderate degree of radiation damage (estimated from the expansion of unit‐cell parameters, broadening of Raman spectral parameters and density) corresponds well, within the “Sri Lankan trends”, with actinide concentrations, U‐Pb age, and the calculated alpha fluence of 1.66 × 1018 g−1. This, and a (U+Th)/He age of 419 ± 9 Ma (2s), enables us to exclude any unusual thermal history or heat treatment, which could potentially have affected the retention of radiogenic Pb. The oxygen isotope ratio of this zircon is 13.9%o VSMOW suggesting a metamorphic genesis in a marble or calc‐silicate skarn.

Temperature- and solvation-dependent dynamics of liquid sulfur dioxide studied through the ultrafast optical Kerr effect

The ultrafast dynamics of liquid sulphur dioxide have been studied over a wide temperature range and in solution. The optically heterodyne-detected and spatially masked optical Kerr effect (OKE) has been used to record the anisotropic and isotropic third-order responses, respectively. Analysis of the anisotropic response reveals two components, an ultrafast nonexponential relaxation and a slower exponential relaxation. The slower component is well described by the Stokes-Einstein-Debye equation for diffusive orientational relaxation. The simple form of the temperature dependence and the agreement between collective (OKE) and single molecule (e.g., NMR) measurements of the orientational relaxation time suggests that orientational pair correlation is not significant in this liquid. The relative contributions of intermolecular interaction-induced and single-molecule orientational dynamics to the ultrafast part of the spectral density are discussed. Single-molecule librational-orientational dynamics appear to dominate the ultrafast OKE response of liquid SO2. The temperature-dependent OKE data are transformed to the frequency domain to yield the Raman spectral density for the low-frequency intermolecular modes. These are bimodal with the lowest-frequency component arising from diffusive orientational relaxation and a higher-frequency component connected with the ultrafast time-domain response. This component is characterized by a shift to higher frequency at lower temperature. This result is analyzed in terms of a harmonic librational oscillator model, which describes the data accurately. The observed spectral shifts with temperature are ascribed to increasing intermolecular interactions with increasing liquid density. Overall, the dynamics of liquid SO2 are found to be well described in terms of molecular orientational relaxation which is controlled over every relevant time range by intermolecular interactions.

Inter- and Intramolecular Hydrogen Bonding in Phenol Derivatives: A Model System for Poly-l-tyrosine

The ultrafast dynamics of solutions of phenol and two phenol derivatives--hydroquinone (1,4-benzenediol) and pyrocatechol (1,2-benzenediol)--have been studied with Optically Heterodyne-Detected Optical Kerr-Effect (OHD-OKE) spectroscopy. The solvents, methanol and acetonitrile, were selected to provide strong and weak solvent-solute hydrogen-bonding interactions, respectively, while pyrocatechol features an intramolecular hydrogen bond. Together these provide a series of model systems for polypeptides such as polytyrosine, which facilitate the direct study of inter- and intramolecular hydrogen bonding. A broad contribution to the Raman spectral density of the methanol solutions at frequencies between 150 and 300 cm(-1) has been observed that is absent in acetonitrile. This contribution has been assigned to solvent-solute hydrogen-bond stretching vibrations. The OHD-OKE response of poly-L-tyrosine has been measured and was found to contain a similar contribution. Density functional theory geometry optimizations and normal mode calculations have been performed using the B3LYP hybrid functional and 6-311++G** basis set. These have yielded a complete assignment of the low-frequency Raman and far-infrared spectra of pyrocatechol for the first time, which has provided information on the nature of the intramolecular hydrogen bond of pyrocatechol.

Polarization Specific Ultrafast Nuclear Dichroic Responses: Raman Spectral Density Recovery and Coherent Coupling Effects

Abstract The frequency selected dichroic ultrafast responses of neat carbon tetrachloride are reported as a function of pump and probe polarization orientations in a standard two beam experimental configuration. The recovery of the Raman spectral density from these experimental observations is demonstrated. The influence of coherent coupling effects, in this one color, electronically nonresonant class of ultrafast pump–probe experiments is considered. While their contribution to Raman spectral densities via birefringent observations can be neglected, these terms can only be eliminated from the dispersed dichroic technique for Raman spectral density recovery when two-color pump–probe studies are performed.

IR theory of weak H-bonds: Davydov coupling, Fermi resonances and direct relaxations. I. Basis equations within the linear response theory

Infrared and Raman spectral densities of cyclic H-bonded dimers, such as encountered in carboxylic acids, are obtained in a full quantum mechanical way by introducing relaxation effects towards the surroundings in the model of Wójcik [Mol. Phys. 36 (1978) 1757] which accounts for the possibility of simultaneous Davydov coupling (between the two hydrogen bonds involved in a cyclic dimer) and Fermi coupling (between each hydrogen bond and one or several bending modes). The relaxations of the fast stretching modes of the H-bonds and of the bending modes are assumed to be of direct type, and are taken into account in the spirit of the Green formalism by insertion of imaginary damping parameters in the effective hamiltonians. Then, the spectral density is obtained within the framework of the linear response theory by Fourier transform of the time-dependent autocorrelation function either of the dipole moment operator, in the infrared case, or of the tensor of the polarizabilities in the Raman case. Extension to non-resonant fast stretching and bending modes, and to several Fermi resonances is also performed according to Henri-Rousseau and Chamma [Chem. Phys. 229 (1998) 37]. In the undamped case, the equivalence of the present work is established with the theory of Maréchal and Witkowski [J. Chem. Phys. 48 (1968) 3697] by neglecting the Fermi resonances. Moreover, one-to-one correspondences are also shown with the work of Henri-Rousseau and Chamma [Chem. Phys. 229 (1998) 37] by ignoring Davydov coupling, and with that of Rösch and Ratner [J. Chem. Phys. 61 (1974) 3344] by neglecting both Davydov and Fermi couplings. Finally, the use of the symmetry properties which appear in cyclic dimers when neglecting the Fermi resonances, initially performed by Maréchal and Witkowski [J. Chem. Phys. 48 (1968) 3697], is discussed, showing the equivalence with the results of the non-symmetrized treatment.

Complete Determination of Intermolecular Spectral Densities of Liquids Using Position-Sensitive Kerr Lens Spectroscopy

Femtosecond position-sensitive Kerr lens spectroscopy is demonstrated to facilitate the direct and complete measurement of the third-order material response function, R(3)(t). The real parts of tensor element response, (t) and (t), for liquid CS2 have been measured and are quantitatively compared to the optical Kerr effect response, (t) + (t). The intermolecular Raman spectral densities are also obtained for each tensor element through Fourier transform. The relationship among these spectral densities is discussed with regard to the nature of the underlying intermolecular motions in liquid CS2. Specifically, we find that the intermolecular depolarization ratio is frequency independent with a value of 0.7 ± 0.1 in the 0−150 cm-1 region.

Electron-vibration coupling in a dynamical fractal: Superionic borate glasses

Abstract In this paper we present the results of a study of the effects of dynamical fractality on vibrational dynamics and electron-vibration coupling in AgI-doped borate glasses, namely the compounds (AgI)x(Ag2O-nB2O3)l-x, with n=1 and x = 0.4, 055 and 0.65. The samples were studied by time-of-flight inelastic neutron scattering and by Raman scattering at several temperatures. Particular care was given to obtain a precise and reliable spectral density with both techniques in the low-frequency range, namely about 1 to about 8O cm−1. In this range, clear indications of fractality were obtained from the anomalous behaviour of the vibrational density g N(ω) of states obtained by neutron scattering. In the same region we also observed a scaling behaviour of the electron-vibration coupling function, obtained from the ratio of the Raman spectral density g R(ω) to the neutron spectral density. g N(ω) was found to be essentially independent of temperature, whereas g N(ω) featured significant changes in the regio...

ChemInform Abstract: LOW‐FREQUENCY RAMAN SCATTERING AND GLASS TRANSITIONS IN ALKALI METAPHOSPHATE GLASSES

An investigation of the low frequency Raman scattering spectra of the alkali metaphosphate glasses (MPO3)n (M=Li,Na,K,Cs) has revealed in the calculated Raman spectral density of states a low frequency band of oscillators between 30 and 70 cm−1. The frequency of the band maxima were found to vary directly as the metal–oxygen force constant and as the inverse of the square of the metal–oxygen separation. The analogous bands in the devitrified glass, or crystal, spectra were not observed and they are assigned as the librational motion of the metaphosphate groups about the metal cation sites in the glass induced by the disorder. A linear relationship between the glass transition temperatures and the frequencies of the band maxima is demonstrated. An analysis of the results has suggested that the glass transformation occurs when sufficient thermal excitation of these oscillators results in exceeding an energy barrier necessary for the rearrangements of the metaphosphate groups about the cation in the glass. T...

Low frequency Raman scattering and glass transitions in alkali metaphosphate glasses

An investigation of the low frequency Raman scattering spectra of the alkali metaphosphate glasses (MPO3)n (M=Li,Na,K,Cs) has revealed in the calculated Raman spectral density of states a low frequency band of oscillators between 30 and 70 cm−1. The frequency of the band maxima were found to vary directly as the metal–oxygen force constant and as the inverse of the square of the metal–oxygen separation. The analogous bands in the devitrified glass, or crystal, spectra were not observed and they are assigned as the librational motion of the metaphosphate groups about the metal cation sites in the glass induced by the disorder. A linear relationship between the glass transition temperatures and the frequencies of the band maxima is demonstrated. An analysis of the results has suggested that the glass transformation occurs when sufficient thermal excitation of these oscillators results in exceeding an energy barrier necessary for the rearrangements of the metaphosphate groups about the cation in the glass. The results also illustrate that differences between the glass transition temperatures of amorphous P2O5 and each of the glasses in the series arises directly from the differences in the zero point energy contributions of the low frequency mode to the internal energy of these materials.

Two-magnon Raman spectra in a spin-one ferromagnetic fcc lattice

We calculate the Raman spectral density of states for quadrupolar excitations in a face-centered-cubic ferromagnetic lattice of spin-one ions with single-ion anisotropy in addition to the isotropic dipolar and quadrupolar pair interactions. We show that the qualitative features of the variation of the Raman spectra with $\ensuremath{\beta}$ (the ratio of the quadrupolar and dipolar coupling) and $d$ (the ratio of the single-ion anisotropy and dipolar coupling) are the same for fcc and sc lattices. In particular, there is always a distinctive peak near the energy for quadrupolar excitation at the zone center, i.e., $2z{\ensuremath{\Gamma}}^{(1)}(1\ensuremath{-}\ensuremath{\beta})$.