Telecom-grade fiber laser-based difference-frequency generation and ppb-level detection of benzene vapor in air around 3 μm

We report on the development of a field deployable compact laser instrument tunable over ∼232 cm⁻¹ from 3.16 to 3.41 μm (2932.5–3164.5 cm⁻¹) for chemical species monitoring at the ppb-level. The laser instrument is based on widely tunable continuous-wave difference-frequency generation (DFG), pumped by two telecom-grade fiber lasers. DFG power of ∼0.3 mW near 3.3 μm with a spectral purity of ∼3.3 MHz was achieved by using moderate pumping powers: 408 mW at 1062 nm and 636 mW at 1570 nm. Spectroscopic performance of the developed DFG-based instrument was evaluated with direct absorption spectra of ethylene at 3.23 μm (∼3094.31 cm⁻¹). Absorption spectra of vapor-phase benzene near 3.28 μm (∼3043.82 cm⁻¹) were recorded with Doppler-limited resolution. Line intensities of the most intense absorption lines of the ν ₁₂ band near 3043.8 cm⁻¹ were determined to support development of sensitive mid-infrared trace gas detection of benzene vapor in the atmosphere. Detection of benzene vapor in air at different concentration levels has been performed for the first time using multi-pass cell enhanced direct absorption spectroscopy at ∼3.28 μm with a minimum detectable concentration of 50 ppb (1σ).     

Coherent laser spectroscopy of RF resonances in liquid

Four-photon polarization spectra of double distilled water subjected to a special treatment in a cavitation chamber and 20% aqueous solution of hydrogen peroxide were recorded in the range ±8 cm⁻¹. All recorded spectra contain narrow (< 0.3 cm⁻¹) resonances corresponding to the frequencies of the rotational spectrum of ortho and para spin isomers of the H₂O molecule. Numerical simulation of the spectra obtained made it possible to quantitatively estimate the contribution of the rotational spectrum to the coherent scattering signal. It was found that the contribution of the para spin isomer of the H₂O molecule to the rotational line spectrum decreases in an aqueous solution of the α-chymotrypsin protein. Apparently, this decrease indicates the selectivity of interaction of biopolymer molecules with different spin isomers.     

FTIR spectra of plasticized high molecular weight PVC–LiCF3SO3 electrolytes

Fourier transform infrared spectroscopy studies have been conducted to investigate the interaction among components in a system of high molecular weight polyvinylchloride (PVC)–lithium trifluoromethanesulfonate (LiCF₃SO₃) incorporated with different type of plasticizers, namely, ethylene carbonate (EC), propylene carbonate (PC), and dibutylphthalate (DBP). Interaction between PVC and LiCF₃SO₃ was confirmed by C–H rocking mode at 1,255 cm⁻¹ for PVC shift to 1,252 cm⁻¹ in PVC–LiCF₃SO₃. The plasticizers’ carbonyl (C=O) oxygen atom which carries lone pair electrons interact with Li⁺ of LiCF₃SO₃ and methine hydrogen of PVC in LiCF₃SO₃–plasticizer system and PVC–plasticizer system, respectively. Changes in peaks assigned to 1,264 cm⁻¹ (ν _as(SO₃)), 1,033 cm⁻¹ (ν _s(SO₃)), 1,181 cm⁻¹ (ν _as(CF₃)), 1,230 cm⁻¹ (ν _s(CF₃)), 765 cm⁻¹ (δ _s(CF₃)), 644 cm⁻¹ (δ _s(SO₃)), 578 cm⁻¹ (δ _as(CF₃)), and 519 cm⁻¹ (δ _as(SO₃)) indicate the occurrence of complexation in the PVC–LiCF₃SO₃ system, LiCF₃SO₃–plasticizer system, and PVC–LiCF₃SO₃–plasticizer system.     

Spectral properties of backward stimulated scattering in liquid carbon disulfide

The spectral structure of backward stimulated scattering from a 10 cm-long CS₂-liquid cell is investigated by using Q-switched 10-ns and 532-nm laser pulses with different spectral linewidths. Under a narrow spectral line (∼0.1 cm⁻¹) pump condition, very strong sharp lines near the pump wavelength (λ ₀) position and the first-order stimulated Raman scattering (λ _s1) position can be observed. However, under a wide line (≈1 cm⁻¹) pump condition, only a strong and superbroadening spectral band can be observed mainly in the red-shift side of the pump wavelength. The different spectral features under these two conditions can be explained by a competition between stimulated Brillouin, Raman, and Rayleigh-Kerr scattering. Under both pump conditions, the broadening spectral distributions are not consistent with the predictions given by stimulated Rayleigh-wing scattering theories, but can be interpreted well utilizing the theoretical model of stimulated Rayleigh-Kerr scattering. Zh. éksp. Teor. Fiz. 112, 1563–1573 (November 1997) Published in English in the original Russian journal. Reproduced here with stylistic changes by the Translation Editor.     

Generation of coherent thermal phonons in amorphous dielectrics at room temperature induced by four-photon interaction

Resonant responses of Mandelshtam-Brillouin scattering from longitudinal and transverse acoustic waves at frequencies of ν _LS = ±1.15 cm⁻¹ and ν _TS = ±0.7 cm⁻¹, respectively, and at frequency of ν _SS = ν _TS $ \sqrt 3 $ \sqrt 3 = ±0.43 cm⁻¹ were detected in K8 optical glass at room temperature using four-photon spectroscopy. We attribute this effect to the induced generation of a second sound wave (coherent thermal phonons). The mechanisms of generation and the possibility of practical application of the observed effect for express diagnostics of the quality of transparent materials are discussed.     

Continuous-wave cavity-ringdown detection of stimulated Raman gain spectra

Cavity ringdown (CRD) spectroscopy, with its high sensitivity, provides a novel way to perform continuous-wave (cw) stimulated Raman gain (SRG) spectroscopy, rather than by conventional optically detected coherent Raman techniques. Tunable cw laser light at ∼1544 nm is used to probe ringdown decay from a rapidly-swept, high-finesse optical cavity containing a gas-phase sample of interest and itself located inside the cavity of a cw single-longitudinal-mode Nd:YAG ring laser operating at ∼1064.4 nm. This approach is used to measure cw SRG spectra of the ν ₁ fundamental rovibrational Raman band of methane gas at ∼2916.5 cm⁻¹. The resulting SRG-CRD resonances have ringdown times longer than in the off-resonance case, in contrast to the usual shorter ringdown times arising from absorption and other loss processes. Previously reported noise-equivalent sensitivities have been substantially improved, by using a second ringdown cavity to facilitate subtraction of infrared-absorption background signals. Moreover, by employing a ringdown cavity in the form of a ring, the SRG-pump and CRD-detected Stokes beams can co-propagate uni-directionally, which significantly reduces Doppler broadening.     

Experimental study of optical gas-dynamic processes of polymeric material ablation by ultrashort laser pulses

Optical gas-dynamic processes occurring in polymeric targets ((CH₂O) _n , (C₂F₄) _n ) exposed to ultrashort laser pulses (τ _0.5 ∼ 45 − 70 fs; λ _I,II,III = 266, 400, 800 nm; and E/S ∼ 0.1 − 40 J/cm² at r ₀ ∼ 20 μm) were studied under normal conditions and in vacuum (p ∼ 10⁻² Pa). The dynamics of the mass flow from the target surface (m′ ∼ 10⁻⁵ − 10⁻⁴ g/J) was studied and the spectral-energy thresholds of laser ablation, the electron density distribution (n _e ∼ 10¹⁴ − 10¹⁸ cm⁻³), the mass-averaged velocity of the material flow from the target surface (∼ 10³ m/s), and the chemical composition and average temperature in the near-surface plasma formation (T ∼ 5000 K) were determined using interference microscopy, emission spectroscopy, and shadowgraphy.     

Spectroscopic study ofβ-Ni(OH)2 under pressure

Infrared absorption and Raman study ofβ-Ni(OH)₂ has been carried out up to 25 GPa and 33 GPa, respectively. The frequency ofA _2u internal antisymmetric stretching O-H mode decreases linearly with pressure at a rate of −0.7 cm⁻1/GPa. The FWHM of this mode increases continuously with pressure and reaches a value of ∼ 120 cm⁻¹ around 25 GPa. There was no discernible change observed in the frequency and width of the symmetric stretchingA _1g O-H Raman mode up to 33 GPa. The constancy of the Raman mode is taken as a signature of the repulsion produced by H-H contacts in this material under pressure. Lack of any discontinuity in these modes suggests that there is no phase transition in this material in the measured pressure range.     

The infrared and laser Raman spectra of K2Zn(SO4)2 · 6H2O

The Raman spectra of the single crystal of K₂Zn(SO₄)₂·6H₂O belonging toC _2h ⁵ space group in the 40–1200 cm⁻¹ region in different scattering geometries and their spectra ofthe microcrystalline salt in the 1500-50 cm⁻¹ region have been reported. The dynamics of the crystal has been described in terms of 186 phonon modes under the unit cell approximation. The weak bands in the region 400–900 cm⁻¹ have been assigned to the libratory modes of H₂O molecules in contradiction to the assignments reported by Ananthanarayanan. The ambiguities existing in the literature about the assignments ofν ₂ ^c andν ₅ ^c modes of [Zn(H₂O)₆]²⁺ have also been removed. The translatory and libratory modes of different units of the crystal have been identified and assignments are made using farir and Raman data on various isomorphous tutton salts. It has been inferred that both SO ₄ ²⁻ tetrahedron and [Zn(H₂O)₆]²⁺ octahedron undergo linear as well as angular distortions from their free state symmetries in the crystal.     

Spectral characteristics of heterocyclic compounds with a chain structure, cooled in an ultrasonic jet

We have recorded the fluorescence excitation spectra of three heterocyclic compounds with a chain structure [BPO (2-phenyl-5-(4-diphenylyl)oxazole), POPOP (1,4-di[2-(5-phenyloxazolyl)]benzene, and TOPOT (1,4-di[2-(5-n-tolyloxazolyl)]benzene] and the fluorescence spectra of POPOP, under conditions where the molecules were cooled in an ultrasonic helium jet. A line structure is observed in the spectra of POPOP and TOPOT; for the BPO molecules, whose configuration changes considerably during electronic excitation, vibrational structure is apparent only in the low-frequency region of the excitation spectrum, and a diffuse spectrum is recorded starting from ν ₀ ⁰ + 200 cm⁻¹. For all the compounds, in the spectra we recorded vibrations with frequencies up to 100 cm⁻¹, arising due to the flexibility of the molecular structure. The rotational contours of the lines for the electronic and vibronic transitions of the POPOP molecules (T_rot = 10.5 K) and TOPOT molecules (T_rot = 15 K) are structureless and bell-shaped. The degree of polarization of the fluorescence P_fl for the jet-cooled POPOP molecules for excitation of vibrations along the absorption band up to 2000 cm⁻¹ above ν ₀ ⁰ is practically constant (∼8.4%) and matches P_fl for high-temperature vapors. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 6, pp. 728–734, November–December, 2006.     

Polarized Raman spectroscopy study of NiSi film grown on Si(001) substrate

We report on the growth of NiSi film on Si(001) substrate with an orientation of NiSi[200]//Si[001]. Polarized Raman spectroscopy was used to assign the symmetry of the NiSi Raman peaks. Raman peaks at 213 cm⁻¹, 295 cm⁻¹, and 367 cm⁻¹ are assigned to be A _g symmetry and peaks at 196 cm⁻¹, and 254 cm⁻¹ are B _3g symmetry.     

Raman scattering by hot polaritons in NaClO3

Summary By nonlinear mixing of IR and visible radiation,i.e. coherent Raman scattering by polaritons driven by a CO₂ laser, it has been possible to get high-resolution spectra for theF-modes of a NaClO₃ crystal in the region (907÷957) cm⁻¹, where several isotopic modes are present. The obtained independent measurement of the refractive index and absorbance allows an accurate determination of the polariton dispersion curve and its width inq-space. The experimental data confirm the existence of a localized isotopic mode at 931 cm⁻¹ and a strongly damped isotopic mode near 960 cm⁻¹. Finally, an accurate measurement of the dispersion of the second-order nonlinear polarizability in the same energy region has been obtained for the first time. This work was supported by the Italian Consiglio Nazionale delle Ricerche and Ministero della Pubblica Istruzione.     

Infrared spectra of BeSO4.4H2O and its deuterated analogue in 4000–1200 cm−1 region

IR spectra of BeSO₄.4H₂O and its deuterated analogue at ∼300 K and ∼110 K are reported in the region 4000–1200 cm⁻¹ using thin film and nujol mull techniques. The observed bands have been assigned as the internal modes of the water and the overtones and combinations of various modes using the recently revised assignments of SO₄ ²⁻ and Be(aq)₄ fundamentals in the region 1200–250 cm⁻¹ (Srivastavaet al 1976). The splitting of the internal modes of water has been discussed in the light of the effects of deuteration and cooling and it is shown that all the water molecules in a unit cell are asymmetric but crystallographically equivalent.     

High-resolution coherent stokes Raman spectroscopy of theν 1 andν 3 bands of methane

Coherent Stokes Raman spectra of the ν₁ and ν₃ bands of CH₄ have been recorded in mixing two pulsed lasers (ruby and dye) of very good spectral and spatial quality. The results show a resolution of about 0.010 cm⁻¹ for a 10 Torr pressure, corresponding in great part to Doppler broadening.     

Dielectric properties of nanometer-thick barium-strontium titanate films

Using submillimeter and infrared spectroscopies, the reflectance R(ν) and transmittance T(ν) spectra of heteroepitaxial barium-strontium titanate films of different thicknesses on MgO substrates are taken for the first time in the frequency range 10 < ν < 3000 cm⁻¹. By modeling the experimental spectra by the Fresnel formulas for layered media, the spectra of complex permittivity ɛ*(ν) = ɛ′(ν) + iɛ″(ν) of the films are determined. It is shown that when the film thicknesses decrease down to 10 nm, there appear tensile stresses in the direction parallel to the substrate surface. As a result, the dielectric contribution of a low-frequency soft mode becomes several times larger than before.     

Influence of anisotropy on the dispersion of surface plasmon-phonon polaritons in silicon carbide

Surface plasmon-phonon polaritons (SPPP’s) of types 3 and 4 are investigated in doped anisotropic single crystals of hexagonal silicon carbide (6H-SiC) in the orientation corresponding to K⊥C and xy⊥C. It is shown that a dispersion dependence of the type-3 SPPP’s bounded by K appears in 6H-SiC when the plasmon frequency increases to ν _p⊥⩾350 cm⁻¹. At ν _p⊥⩾400 cm⁻¹, ν _s(K) exists for type-4 SPPP’s in the frequency range Ω _∥ ⁺ <ν< _⊥ ⁺ . When the concentration of free charge carriers is increased, the dispersion curves are displaced toward higher frequencies. The conditions for the existence of type-3 and type-4 SPPP’s in 6H-SiC are determined. Fiz. Tverd. Tela (St. Petersburg) 40, 636–639 (April 1998)     

Effect of plasmon-phonon excitations on the coefficient of reflection from the surface of hexagonal silicon carbide

The coefficient R(ν) of reflection from the surface of 6H-SiC single crystals is studied in the case in which the long-wavelength optical vibrations of the lattice are coupled with the electron plasma. It is shown for the first time that the anisotropy of the properties of electrons and phonons in 6H-SiC gives rise to special features in the spectrum of the coupled vibrations and the transparency regions. It is found, in particular, that if the axis of the crystal lies in the polarization plane of the incident radiation (0<θ<90°), for 30 cm⁻¹⩽ν _p⊥<320 cm⁻¹ the spectrum of R(ν) acquires three regions of transparency and opacity, and for ν _p⊥⩾320 cm⁻¹ four such regions, which are absent in an isotropic medium. The width of these regions is found to depend on the electron concentration in the conduction band and on the angle θ. Zh. éksp. Teor. Fiz. 116, 646–654 (August 1999)     

High resolution,rotation, vibration spectra of D2O in the region ofν 1 andν 3 bands

The infrared spectrum of D₂O from 2400 to 3000 cm⁻¹ has been analysed at a resolution better than 0·02 cm⁻¹. It was recorded at the Fourier transform spectrometer of the Kitt Peak National Observatory, Tucson. Ground state constants of the reduced Watson-Hamiltonian, ground state energies and transition for theν ₁ andν ₃ bands are reported. The effect of strong Coriolis resonances on the spectra is discussed. Work done at the Jet Propulsion Laboratory, Division of Stratospheric and Planetary Research California Institute of Technology, Pasadena, Ca (U.S.A.)     

Vibrational spectrum of perfluoroethane

We have obtained IR absorption spectra of a C₂F₆ gas and a C₂F₆ cryosolution in Xe (T = 163 K) in the fundamental and overtone ranges. We have interpreted 28 bands of ¹²C¹²CF₆ and three bands of ¹³C¹²CF₆. In the spectral ranges that correspond to vibrations that are combinations with ν₁, ν₇, and ν₅, we observe multiplets, which we attribute to interactions of the type of Fermi resonances between the states ν₁(A _1g ) ∼ ν₆(A _1g ), ν₇(E _g ) ∼ ν₆ + ν₁₁(E _g ) ∼ 2ν₈(E _g ), ν₅(A _2u ) ∼ ν₈ + ν ₁₁(A _2u ). We reveal an anomalous intensity distribution in the spectrum of an asymmetric isotopologue. For the basic and isotopic configurations of perfluoroethane, we calculate the coefficients of shapes of vibrations and the intensities of absorption bands. We reveal that the behavior of the groups ¹²CF₃ and ¹³CF₃ is indifferent to the excitation of doubly degenerate stretching vibrations ν₇(E _g ) and ν₁₀(Eu).     

Critical current densities of high pressure oxygen sputtered thin films of YBa2Cu3O7−x by non-resonant rf absorption method

The critical current densities (J _c) have been measured at 77K in high pressure oxygen sputtered thin films of YBa₂Cu₃O_7−x superconductor using the non-resonant rf absorption technique. High values ofJ _c (∼ 10⁵ A/cm²) are observed in these relatively large area (∼ 1·2 cm²) films.