Nonlinear transformation of a spectrum of femtosecond laser pulses in a gas-filled microcapillary

Features of light pulse propagation and nonlinear optical transformation of the spectrum generated by titanium-sapphire laser pulses (τ_0.5 = 27 fs, λ₀ = 790 nm) have been studied experimentally in a 50-cm cylindrical hollow waveguide (microcapillary with 280-μm diameter core) filled with gaseous molecular nitrogen and helium. Stable guided propagation of light pulses with an intensity of ~1.5⋅10¹⁴ W/cm² in the fundamental EH₁₁ mode of the gas-filled capillary has been demonstrated. Exact focusing of the laser light made it possible to obtain rather high relative (≥95%) and absolute (~60%) energy transmission efficiencies for the pulses at gas pressures equal to or lower than 760 Torr. A method to determine the nonlinear phase shift of the pulses has been proposed. Values of the nonlinear refractive index n₂ ≈ 4.5⋅10^–23 cm²/(W⋅Torr) (N₂) and n₂ ≈ 2.8⋅10^–23 cm²/(W⋅Torr) (He) have been found. A short-wavelength shift in addition to the Kerr nonlinearity has been shown to be contributed by the generated electron plasma at high pulse intensities (≥10¹⁴ W/cm²).     

The growth of Y2SiO5:Ce thin films with pulsed laser deposition

Y₂SiO₅:Ce phosphor thin films were grown onto Si(100) substrates with pulsed laser deposition (PLD) using a 248-nm KrF excimer laser. Process parameters were varied during the growth process and the effect on the surface morphology and cathodoluminescence (CL) was analysed. The process parameters that were changed included the following: gas pressure (vacuum (5×10⁻⁶ Torr), 1×1⁻² Torr and 1 Torr O₂), different gas species (O₂, Ar and N₂ at a pressure of 455 mTorr), laser fluence (1.6±0.1 J cm⁻² and 3.0±0.3 J cm⁻²) and substrate temperature (400 and 600°C). The surface morphology was investigated with atomic force microscopy (AFM). The morphology of the thin films ablated in vacuum and 10 mTorr ambient O₂ showed more or less the same trend. An increase in the pressure to 1 Torr O₂, however, showed a definite increase in deposited particle sizes. Ablation in N₂ gas resulted in small particles of 20 nm in diameter and ablation in O₂ gas produced bigger particles of 20, 30 and 40 nm as well as an agglomeration of these particles into bigger size clusters of 80 to 100 nm. Ablation in Ar gas led to particle sizes of 30 nm and the particles were much more spherically defined and evenly distributed on the surface. The higher fluence deposition led to bigger particle and grain sizes as well as thicker layers with respect to the lower fluence. The particle sizes of the higher fluence vary mainly between 130 and 140 nm and the lower fluence sizes vary between 50 and 60 nm. The higher fluence particles consist of smaller particles ranging from 5 to 30 nm as measured with AFM. The surface structure of the thin film ablated at 400°C substrate temperature is less compact (lesser agglomeration of particles than at 600°C). The increase in substrate temperature definitely resulted in a rougher surface layer. CL was measured to investigate the effect of the surface morphology on the luminescent intensities. The increased O₂ ambient (1 Torr) resulted in a higher CL intensity compared to the thin films ablated in vacuum. The thin film ablated in Ar gas showed a much higher CL intensity than the other thin films. Ablation at a high fluence resulted in a higher CL intensity. The higher substrate temperature resulted in better CL intensities. The more spherically shaped particles and rougher surface led to increase CL intensities.     

Role of highly efficient collisions in collisional transfer of vibrational energy in benzophenone-foreign gas mixtures

Collisional losses of vibrational energy in mixtures of benzophenone excited by nitrogen laser radiation (λ=337 nm) and foreign gases (Ar, Kr, SF₆, C₅H₁₂) were studied by time-resolved delayed luminescence. It is established that the intensities and rates of decay of the fast and slow components of delayed luminescence can be used to evaluate the characteristics of V–V– and V–T–transfer of vibrational energy. For the V-V-process, the efficiencies and mean energies transferred in a collision are determined. It is shown that in the mixture with multiatomic gases, vibrational equilibrium is reached after a few collisions, the number of which decreases as the molecule of the foreign gas becomes more complicated. The V–V–process is characterized by high efficiencies of collisions typical for “supercollisions”. The experimental characteristics of V-V-transfer correlate well with ergodic transfer of vibrational energy predicted by statistical theories. 0120 0126 V 3 Institute of Molecular and Atomic Physics of the National Academy of Science of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 3, pp. 340–345, May–June, 1998.     

Resonance photoacoustic spectroscopy and gas analysis of gaseous flow at reduced pressure

The results of theoretical and experimental studies of sensitivity of a resonant photoacoustic Helmholtz resonator detector for gas flowing through a photoacoustic cell under reduced pressure are presented. The measurements of the sensitivity and ultimate sensitivity of the differential photoacoustic cell were performed with a near-IR room-temperature diode laser using the well-known H₂O absorption line (12496.1056 cm^-1) as a reference. The measured value of the sensitivity (6–17 Pa W m^-1) is in satisfactory agreement with the calculated one, which equals 6–35 Pa W m^-1. The obtained value of the ultimate sensitivity ((3–5)×10^-7 W m^-1 Hz^-1/2) provides measurements of the concentration of molecules at the ppb–ppm level. Received: 19 April 2001 / Revised version: 18 September 2001 / Published online: 7 November 2001     

Characterization of a Br(2P1/2)–CO2(1001-1000) transfer laser driven by photolysis of iodine monobromide

2 laser operating on the 10⁰1-10⁰0 transition at λ=4.3 μm and pumped by E –V energy transfer from Br(²P_1/2) has been demonstrated. The dynamics and performance of this device were characterized by observing the time-resolved stimulated emission and the steady-state spontaneous side fluorescence after photolysis of IBr or Br₂ by a frequency-doubled Nd:YAG laser or Ar⁺ laser, respectively. Although the E –V excitation kinetics are favorable, rapid vibrational relaxation limits laser action to CO₂ pressures of less than 1 Torr. Numerical modeling of laser pulse shapes and the dependence on IBr and CO₂ pressure and photolysis energy establish a relatively high gain of 0.33%/cm, a CO₂-pressure-dependent optical loss of 0.04–0.06%/cm, and an efficiency of 2×10^-5 4.3-μm-laser photons per incident photolysis photon. The CO₂ fluorescence after photolysis of a fixed Br₂/CO₂ gas mixture decreases as a function of photolysis time by about 30%/h, indicating the photolytic production of an important quencher. Received: 23 June 1997/Revised version: 23 September 1997     

Pulsed laser deposition of Zr–N codoped <Emphasis Type="Italic">p</Emphasis>-type ZnO thin films

Present p-type ZnO films tend to exhibit high resistivity and low carrier concentration, and they revert to their natural n-type state within days after deposition. One approach to grow higher quality p-type ZnO is by codoping the ZnO during growth. This article describes recent results from the growth and characterization of Zr–N codoped p-type ZnO thin films by pulsed laser deposition (PLD) on (0001) sapphire substrates. For this work, both N-doped and Zr–N codoped p-type ZnO films were grown for comparison purposes at substrate temperatures ranging between 400 to 700 °C and N₂O background pressures between 10⁻⁵ to 10⁻² Torr. The carrier type and conduction were found to be very sensitive to substrate temperature and N₂O deposition pressure. P-type conduction was observed for films grown at pressures between 10⁻³ to 10⁻² Torr. The Zr–N codoped ZnO films grown at 550 °C in 1×10⁻³ Torr of N₂O show p-type conduction behavior with a very low resistivity of 0.89 Ω-cm, a carrier concentration of 5.0×10¹⁸ cm⁻³, and a Hall mobility of 1.4 cm² V⁻¹ s⁻¹. The structure, morphology and optical properties were also evaluated for both N-doped and Zr–N codoped ZnO films.     

Effect of gas pressure and pulse length on the isotopically selective multiphoton dissociation of CF3Cl under CO2 laser pulses

The multiphoton dissociation of CF₃Cl induced by TEA-CO₂ laser pulses has been studied in a focused beam geometry. TheR(10) [00°1–02°0] ( ) laser line was used, so as to dissociate preferentially the minor isotopic component¹³CF₃Cl. The isotopic selectivityS and the dissociation probability per pulse ω were measured in the pressure range between 0.25 and 8 Torr. With short laser pulses (90 ns FWHM),S is found to increase slightly with gas pressure up to 2 Torr, and ω, to increase almost linearly over the whole pressure range studied. A schematic model is proposed which satisfactorily explains these results if the transition rates across the energy level spectrum of the CF₃Cl molecules are assumed to increase with gas pressure.     

Gas temperature measurements using widely tunable long-wavelength VCSEL

A method for gas temperature measurements with a widely tunable laser diode is presented. The method involves rapidly switching the laser frequency between two distantly spaced absorption lines chosen for optical thermometry. Direct absorption spectroscopy using a single-mode VCSEL was employed to probe the R10 and R22 lines of the 2ν₁+2ν₂ ⁰+ν₃ combination band of CO₂ near 6355.9 and 6363.7 cm^-1 sequentially. A specially designed 0.5-m cryogenic gas cell was filled with 10 mbar CO₂ at room temperature and cooled to 150 K with liquid N₂. The VCSEL was modulated with a 10-kHz ramp superimposed on a 1-kHz square waveform to scan two 0.04 cm^-1 intervals sequentially. The gas temperatures obtained with the VCSEL in the 150–300 K range are in a good agreement with those derived from gas pressure ratios. The maximum relative error of temperature measurements using the VCSEL was ± 3%. A compact VCSEL-based sensor can be developed for gas temperature and concentration measurements in the Martian atmosphere. The method proposed can be used for many applications including in situ monitoring of combustion processes. PACS 42.62.Fi; 42.55.Px; 39.30.+w     

Diffusion study of <Superscript>15</Superscript>N implanted into α-Ti using the nuclear resonance technique

The diffusion of ¹⁵N in α-Ti was studied in the 673–1023 K temperature range by using the ion implantation and nuclear resonance techniques. The measurements show that the diffusion coefficients follow an Arrhenius behavior D(T)=D₀ ^-Q/RT, where D₀=(1.1±0.8)×10^-7 m² s^-1 and Q=(183±2) kJ/mol. A comparison with previous results is also given. PACS 66.30.Jt; 85.40.Ry     

An off-axis cavity-enhanced absorption spectrometer at 1605 nm for the 12CO2/13CO2 measurement

A distributed feedback diode laser sensor based upon off-axis cavity-enhanced absorption spectroscopy at 1605.5 nm has been developed for ¹³C¹⁶O₂/¹²C¹⁶O₂ isotope ratio measurements in synthetic air and human breath. A noise-equivalent absorption sensitivity of 3.9×10^-10 cm^-1 Hz^-1/2 has been determined for a cavity base length of 28.2 cm and averaging 4000 scans within 8.688 s. For 5% CO₂ concentration measurements, δ¹³C standard deviations of 1.8 ‰ and 3.7 ‰ have been estimated for five successive measurements based on peak height and integrated area estimations at 107.9 Torr, respectively. The contributions of amplified spontaneous emission of the laser and a radiation that is spatially uncoupled into the cavity mode have been described for cavity transmittance measurements. The limitations of the developed sensor and further steps towards precision and accuracy improvements are discussed. PACS 42.55.Px; 39.30.+w; 42.62.Fi; 42.60.-v     

Interaction of ethidium bromide and caffeine with DNA in aqueous solution

Two component (ethidium bromide–caffeine, ethidium bromide–DNA) and three component (ethidium bromide–caffeine–DNA) systems in aqueous saline (0.01 M NaCl) phosphate buffer solutions (pH 6.86, T = 298 K) are studied spectrophotometrically. The equilibrium constants for dimerization of caffeine, K _D  = 1.22 ± 2 M⁻¹, and for heteroassociation of ethidium bromide with caffeine, K = 71 ± 8 M⁻¹, in ethidium bromide–caffeine systems are determined. When the concentration of caffeine is increased, the dynamic equilibrium of the solution shifts toward formation of heterocomplexes which are, presumably, stabilized by dispersive and hydrophobic interactions of chromophores. The equilibrium parameters for ethidium bromide complex formation with DNA are calculated: the coupling constant for the dye with the biopolymer, K ₁ = (232 ± 16)⋅103 M⁻¹, and the number of base pairs of the biopolymer participating in bonding with the ligand, n ₁ = 3.6 ± 0.2, are calculated. Given these values, it is suggested that under these experimental conditions there are two types of bonding between ethidium bromide and the nucleic acid — intercalation and “external” bonds. A McGhee–von Hippel model for a three component system and the numerical values of the parameters for molecular complex formation in two component systems are used to calculate the bonding constant for caffeine with DNA, K ₂ = 127 ± 30 M⁻¹, and the number of base pairs of DNA which bond with caffeine, n ₂ = 1.7 ± 0.2. The concentrations of ethidium bromide and caffeine in the composition of two and three component complexes are calculated as functions of the nucleic acid content in the solution. An analysis of the concentration dependences shows that heteroassociation of ligands has a significant effect on the reduction in the concentration of ethidium bromide–DNA complexes in a three component system for low DNA concentrations, while at high DNA concentrations the bonding of caffeine with the biopolymer has this effect. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 1, pp. 143–151, January–February 2009.     

Association of riboflavin,caffeine, and sodium salicylate in aqueous solution

We have used UV and visible spectrophotometry to study self-association of aromatic riboflavin molecules (RFN, vitamin B₂, 7,8-dimethyl-10-N-(1′-D-ribityl)isoalloxazine) in aqueous solution (pH 6.86) at T = 298 K, using a dimer model. We have determined the equilibrium dimerization constant for riboflavin, K_dB = 125 ± 40 M⁻¹. We have studied heteroassociation in the system of molecules of 7,8-dimethyl-10-ribitylisoalloxazine with 1,3,7-trimethylxanthine (caffeine) and sodium salicylate (NAS) in aqueous solution (pH 6.86; T = 298 K). We have determined the heteroassociation constants for RFN-NAS and RFN-caffeine molecules in the absence and in the presence of urea in solutions using a modified Benesi-Hildebrand equation: 25 ± 4, 17 ± 3, and 74 ± 11, 53 ± 7 M⁻¹ respectively. We have determined the dimerization constants for NAS (2.7 ± 0.5 M⁻¹) and caffeine (17.0 ± 1.5 M⁻¹). We conclude that heteroassociation of the aromatic molecules leads to a lower effective riboflavin concentration in solution, and the presence of urea in mixed solutions leads to an decrease in the complexation constants for the RFN-NAS and RFN-caffeine systems. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 188–194, March–April, 2007.     

New Fluorescent Antitumour Cisplatin Analogue Complexes. Study of the Characteristics of their Binding to DNA by Flow Injection Analysis

The flow injection technique is applied to study the binding to DNA of new platinum complexes—E₁: ethylenediaminechlorocholylglycinateplatinum(II): [PtCl(CG)(en)], C₅₄H₉₂O₁₂Pt and E₂: ethylenediaminebischolylglycinateplatinum(II): [Pt(CG)₂(en)], C₂₈H₅₀ClN₃O₆Pt—derived from cisplatin in which the exchangeable ligands were replaced by bile acids, such that these anticancer drugs have less toxicity and less resistance is developed towards them. Both compounds are fluorescent and their fluorescence is enhanced when they form adducts with DNA, a property that is extremely useful for monitoring the cytotoxic activity and their mechanisms of action. The binding parameters to DNA of E₁ [apparent intrinsic binding constant K_E1: (11.2 ± 0.4) × 10³ M⁻¹ and maximum number of binding sites per nucleotide, n _E1: 0.121 ± 2 × 10⁻³) and E₂ (K_E2: 9.2 ± 0.7) × 10³ M⁻¹ and n _E2 0.098 ± 2 × 10⁻³] were determined following the Scatchard method and the type of binding was studied experimentally through the modifications introduced by each of the compounds into the ethidium bromide–DNA bond.     

Spectrofluorimetric Assessment of Chlorzoxazone and Ibuprofen in Pharmaceutical Formulations by using Eu-Tetracycline HCl Optical Sensor Doped in Sol–Gel Matrix

A novel, simple, sensitive and selective spectrofluorimetric method was developed for the determination of trace amounts of chlorzoxazone and Ibuprofen in pharmaceutical tablets using optical sensor Eu-Tetracycline HCl doped in sol–gel matrix. The chlorzoxazone or Ibuprofen can remarkably enhance the luminescence intensity of Eu-Tetracycline HCl complex doped in a sol–gel matrix in dimethylformamide (DMF) at pH 9.7 and 6.3, respectively, λ_ex = 400 nm. The enhancing of luminescence intensity peak of Eu-Tetracycline HCl complex at 617 nm is proportional to the concentration of chlorzoxazone or Ibuprofen a result that suggested profitable application as a simple optical sensor for chlorzoxazone or Ibuprofen assessment. The dynamic ranges found for the determination of chlorzoxazone and Ibuprofen concentration are 5 × 10⁻⁹–1 × 10⁻⁴ and 1 × 10⁻⁸–7 × 10⁻⁵ mol L⁻¹, and the limit of detection (LOD) and quantitation limit of detection (LOQ) are 3.1 × 10⁻¹⁰ , 9.6 × 10⁻¹⁰ and 5.6 × 10⁻¹⁰, 1.7 × 10⁻⁹ mol L⁻¹, respectively.     

Limited volume thin film deposition on geometrically complicated substrates

In this paper we report a study on the elastic scattering of electrons by lithium and sodium atoms in the presence of circularly polarized resonant laser field within the framework of the two-state rotating wave approximation. The effect of laser on projectile electrons is described by Volkov states. The frequency of the laser field is chosen to match with the 2s–3p (3s–3p) transition frequency in lithium (sodium) atoms. The total and differential elastic cross sections with single photon exchange are calculated for intermediate energies (50–150 eV) and laser intensity (10⁷–10¹¹ W cm^-2). An erratum to this article can be found online at http://dx.doi.org/. An erratum to this article can be found at     

High resolution ethylene absorption spectrum between 6035 and 6210 cm-1

A two-channel photo-acoustic spectrometer (PA spectrometer) with a near infrared diode laser was used for taking measurements of a high resolution ethylene absorption spectrum. A semiconductor TEC-100 laser with an outer resonator generates a continuous single-frequency radiation in the range 6030–6300 cm^-1. A newly designed model of photo-acoustic detector (PAD) in the form of a ring type resonator provides for measurement of weak absorption cross-section equal to 4×10^-23 cm²/mol at a laser radiation power of 3 mW. The PAD threshold sensitivity is 2×10^-9 cm^-1 Hz^-1/2 W, when the signal to noise ratio equals to 1. The ethylene absorption spectrum within the range 6035–6210 cm^-1 was measured for the first time with a spectral resolution of 10 MHz. The reported line centre positions have an uncertainty of ± 0.0005 cm^-1. The precise measurements of ethylene absorption cross-sections were carried out using the mixture of high purity ethylene and broadening gas (nitrogen) at the mixture ratio 1:50–1:200. Measurements were carried out at a mixture pressure of about 4.2 kPa. PACS 42.62.Fi; 42.55.Px     

Linewidth studies on Cd+ 636.0 nm and 537.8 nm lines excited in a He-Cd hollow cathode discharge

Hollow cathode (HC) lasers usually operate in a single axial mode without any optical selection. This is attributed to the large homogeneous linewidth of the gain curve due to the relatively high filling pressure of these lasers. Collisional and Doppler broadening (Δν_C and Δν_D) of the Cd⁺ 636 nm and Cd⁺ 538 nm lines (laser transitions of the HeCd⁺ laser) excited in a HC discharge tube were determined using a Fabry–Perot interferometer technique. It was found that in the pressure range 7–25 mbar Δν_D was nearly constant, while, as expected, Δν_C increased linearly with pressure. The broadening constants were α(636 nm)= (47±2) MHz/mbarand α(538 nm)=(11.8±0.5) MHz/mbar. The first constant is large enough to explain single-mode operation of the red HeCd⁺ laser; but in the case of the green laser, the exact reason for the single-mode operation remained unclear. Received: 23 November 2000 / Revised version: 30 March 2001 / Published online: 7 June 2001     

A Long Wavelength Excitable Fluorophore; Chloro Phenyl Imino Propenyl Aniline (CPIPA) for Selective Sensing of Hg (II)

In this study, a very sensitive and highly selective irreversible optical chemical sensor (optode) for mercury ions was described. The sensing scheme was based on the interaction of Hg (II) with a newly synthesized fluoroionophore; chloro phenyl imino propenyl aniline (CPIPA) in plasticized PVC membrane. The sensor membranes were tested for the determination of mercury ion in aqueous solutions by batch and flow-through methods. The optodes allow determination of Hg (II) in the working range of 1.0 × 10⁻⁹–1.0 × 10⁻⁵ M with a detection limit of 4.3 ppb. The sensor exhibited excellent selectivity for Hg (II) with respect to several common alkali, alkaline earth and transition metal ions. The association constant of the 1:1 complex formation for Hg (II) was found to be K_a = 1.86 × 10⁵ M⁻¹. The CPIPA exhibited high fluorescence quantum yield, long excitation and emission wavelength and high Stokes’ shift values in the solid matrix which makes it compatible with solid state optics.     

Energy and angular momentum transfer in atom-diatom collisions from polarized laser fluorescence

We report a study of collisional reorientation of diatomic lithium molecules by rare gas atoms using high resolution circularly polarized laser fluorescence. As in the case of I₂ we find that elastic collisions are very inefficient at reorienting Li₂ molecules and a selection rule ΔM′ _J = 0 appears to be in operation. Rotationally inelastic collisions, particularly those with argon, cause some degree of reorientation and are the result of relatively long range intermolecular interactions. Vibrational transfer features are more strongly depolarized. Optical pumping studies of oriented ¹Σ _g Li₂ molecules have yielded a cross section for inelastic transfer of 35 ± 15 Ų.     

Temperature dependence of the quenching of N<Subscript>2</Subscript> (C <Superscript>3</Superscript>Π<Subscript>u</Subscript>) by N<Subscript>2</Subscript> (X) and O<Subscript>2</Subscript> (X)

The temperature dependences of the quenching rate constants of the states N₂ (${\rm C} \ {^{3}{ \rm \Pi }_{u}}${\rm C} \ {^{3}{ \rm \Pi }_{u}} v^′=0,1) by N₂ (X) and of the state N₂ (${\rm C} \ {^{3}{ \rm \Pi }_{u}} \ v^{\prime}=0${\rm C} \ {^{3}{ \rm \Pi }_{u}} \ v^{\prime}=0) by O₂ (X) are studied. Time-resolved light emission from the gas was analyzed in the temperature range from 300 K to 210 K keeping the gas at constant density. In case of quenching by N₂ (X), the quenching rate constant for the vibrational level v^′= 0 increases by (13 ±3)% with gas cooling whereas the quenching rate constant for v^′= 1 decreases by (5.0 ±2.5)% in this temperature range. For quenching by O₂ (X), the quenching rate constant decreases by (3 ±2)% with gas cooling. The temperature variation of the N₂ (C ³Π_u v^′=0) emission intensity for pure nitrogen and dry air are calculated using the obtained quenching rate constants and is compared with the experimental data available in the literature.