Observation of interband two-photon absorption saturation in CdS nanocrystals

We report the observation of interband two-photon absorption (TPA) saturation in cadmium sulfide nanocrystals (CdS NCs) under intense femtosecond laser excitation with 1.6 eV photon energy. The observation has been compared to interband TPA saturation in bulk CdS under the same experimental conditions. By using both Z-scan techniques and transient absorption measurements, the saturation intensity has been determined to be 190 GW/cm2 for CdS NCs of 4-nm diameter, which is 2 orders of magnitude greater than that for CdS bulk crystal. The results are in agreement with an inhomogeneously broadened, saturated TPA model.     

Temperature dependent structured absorption spectra of molecular chlorine

A dual wavelength range spectrometer system has been designed and constructed which can simultaneously perform single pass UV absorption spectroscopy and cavity enhanced absorption spectroscopy in the green region of the visible spectrum. Using the system the absorption spectrum of molecular chlorine has been measured, in the wavelength range 509-570 nm, using cavity enhanced absorption spectroscopy. Absolute absorption cross sections were obtained by simultaneous measurement of the UV spectrum to obtain the Cl(2) concentration. These are the first temperature dependent measurements of the Cl(2) absorption cross sections in this region which are vibronically resolved. Laboratory measurements were conducted at four temperatures (298, 273, 233, and 197 K). Spectral modelling of the Cl(2) B(3)Π(0(u)(+))-X(1)Σ(g)(+) electronic transition has been performed, the results of which are in good agreement with our measured spectra.     

Analytical applications of laser moding caused by intracavity absorption

A continuous CO₂ laser with a reflecting mirror can operate at several wavelengths simultaneously. If an organic vapor is introduced into a separate cavity in the laser optical path, the laser will sometimes mode rapidly causing some lasing lines to diminish to zero and others to become enhanced; this has been observed even for very low amounts (10^-5 g) of organic gases. Laser intercavity absorption spectroscopy depends on overlap of a vibrational—rotational line of a sample with a laser transition line. The absorption by the sample greatly affects the laser wavetrain at that particular wavelength and interferes with the lasing action. The technique is not based on Beer's law, and the detection limits observed are orders of magnitude better than those of conventional infrared absorption spectroscopy. Two laser systems were used and various organic gases were studied. When a totally reflecting mirror which permitted free moding was used, the detection limits found were 0.14 μg, 0.95 μg and 0.60 μg for vinyl chloride, propylene, and ethylene, respectively. When a grating was used as the rear cavity optics restricting the wavelengths of the laser lines, the detection limits were 140 μg, 94 μg, 63 μg and 0.26 μg for vinyl chloride, propylene. ethylene and ethyl chloride, respectively.     

Imaged intracavity laser absorption spectroscopy

Using a laser resonator design which supports many high order transverse modes it is possible to enhance a spatial variation (i.e., an image) as well as a spectral variation in absorption of a sample inside the optical cavity of an organic dye laser. This technique also enhances the practical sensitivity of intracavity absorption spectroscopy.     

Cavity-enhanced absorption using an atomic line source: application to deep-UV measurements

Optical cavities are commonly used to increase the sensitivity of absorption measurements, but have not been extensively used below 300 nm, mainly owing to the limited light sources at these wavelengths. While some progress has been made using cavity ring-down spectroscopy, these systems rely on complex and expensive lasers. Here we investigate an approach combining Cavity-Enhanced Absorption Spectroscopy (CEAS) with an inexpensive low vapour pressure mercury lamp for sensitive absorption measurements at 253.7 nm. We demonstrate that the CEAS absorption in our system is 50 times greater than the absorption found in a single-pass configuration; using this approach, we obtained limits of detection of 8.1 pptv (66 ng m(-3)) for gaseous elemental mercury and 8.4 ppbv for ozone. We evaluate the performance of the system and discuss potential improvements and applications of this approach.     

The detection of carbon monoxide by cavity enhanced absorption spectroscopy with a DFB diode laser

It has been proven that cavity enhanced absorption spectroscopy is a high sensitive spectral technique. The aim of our study was to apply this spectral technique to the detection of carbon monoxide with a narrow line width tunable DFB diode laser and high Q factor optical cavity. Absorption signals were extracted from a measurement recording the average of 20 highest light intensities that leak out of the cavity. The absorption spectrum of CO centered at 6354.18 cm⁻¹ was recorded; the experiment results indicate that cavity enhanced absorption spectroscopy could produce accurate high resolution spectrum. A detection sensitivity about 5.687 × 10⁻⁷ cm⁻¹ has been achieved in a 45 cm-long cell.     

The far-infrared absorption of dichloromethane determined by spot frequency measurements

The absorption of dichloromethane at 298 K has been measured at 14 spot frequencies from 33 to 213 cm⁻¹ using an Apollo far-i.r. laser system with methanol as the lasing gas optically pumped by a 50 W CO₂ laser. The results agree with those obtained by Fourier transform interferometry and allow a greater accuracy in the measurement of absolute intensity and spectral moments for this intensely absorbing liquid. The band profile is rationalized using a three parameter Mori continued fraction with two of the parameters predetermined from knowledge of the Debye relaxation time and the (forth moment) mean square torque.     

Photo-acoustic measurements of gas and aerosol absorption with diode lasers

The results of designing multipurpose high-sensitive photo-acoustic (PA) detectors and their application to high-resolution diode laser spectroscopy of molecular gases, gas analysis, and aerosol absorption measurements are summarized in this paper. The hardware and software of the diode laser spectrometer with a Helmholtz resonant PA detector providing an absorption sensitivity limit of better than 10(-7)Wm(-1)Hz(-1/2) are described. A procedure is proposed for an experiment involving the measurements of the rotational structure of hot vibrational bands of molecules. The results of the application of the nonresonant PA cell with temporal resolution of signals to measurements of weak nonresonant absorption of gases and soot aerosols are presented, and the possibility of creating a broad-band PA laser diode aerosol-meter is discussed.     

Generation of DNA photolesions by two-photon absorption of a frequency-doubled Ti:sapphire laser

The formation of spatially localized regions of DNA damage by multiphoton absorption of light is an attractive tool for investigating DNA repair. Although this method has been applied in cells, little information is available about the formation of lesions by multiphoton absorption in the absence of exogenous or endogenous sensitizing agents. Therefore, we have investigated DNA damage induced in vitro by direct two-photon absorption of frequency-doubled femtosecond pulses from a Ti:sapphire laser. We first developed a quantitative polymerase chain reaction assay to measure DNA damage, and determined that the quantum yield of lesions formed by one-photon absorption of 254 nm light is 7.86×10(-4). We then measured the yield of lesions resulting from exposure to the visible femtosecond laser pulses, which exhibited a quadratic intensity dependence. The two-photon absorption cross section of DNA has a value (per nucleotide) of 2.6 GM at 425 nm, 2.4 GM at 450 nm, and 1.9 GM at 475 nm. A comparison of these in vitro results to several in vivo studies of multiphoton photodamage indicates that the onset of DNA damage occurs at lower intensities in vivo; we suggest possible explanations for this discrepancy.     

Highly accurate determinations of CO(2) line strengths using intensity-stabilized diode laser absorption spectrometry

An intensity-stabilized laser absorption spectrometer, which incorporates a mirror-extended cavity diode laser, a temperature-stabilized gas cell, and a Michelson interferometer, was developed and applied to a highly accurate investigation of line intensity factors within the nu(1)+2nu(2) (0)+nu(3) combination band of carbon dioxide, around 2 microm wavelength, at a temperature of 296.0 K. This relatively complex apparatus enables one to observe the absorption line shape with high precision and accuracy in such a way that it is possible to retrieve the integrated absorbance with a relative uncertainty better than 0.1%. The absorption spectra were interpolated with the uncorrelated strong-collision model of Rautian and Sobel'man in order to take into account Dicke narrowing effects, thus obtaining an agreement at a level of a few parts per 10(-5). We report line strength values for the R(2)-R(18) transitions with an unprecedented level of accuracy, in the range between 0.1% and 0.15%. Finally, we discuss the possibility of providing a first experimental test of the theoretical model for molecular line strengths based on the Herman-Wallis expansion.     

Diode laser atomic absorption spectrometry

The paper reviews the past 11 years of literature on the application of diode lasers in atomic absorption spectrometry with graphite furnaces (GF), plasmas and flames as atomizers. Experimental arrangements and techniques for powerful absorption measurements as well as the theoretical background are covered. The analytical possibilities of high-resolution spectroscopy, including Doppler-free techniques for isotope selective measurements and isotope dilution analysis are discussed and various applications of element-selective detection by diode laser atomic absorption in combination with separation techniques, such as liquid (LC) and gas chromatography (GC), and with laser ablation of solid samples, are presented.     

Non-quadratic-intensity dependence of two-photon absorption induced fluorescence of organic chromophores in solution

We have provided a model to interpret the non-quadratic-intensity dependence behavior commonly observed in the two-photon fluorescence (TPF) experiment excited with high laser intensity. The model also provides one with a different technique to measure the two-photon absorption cross section of an organic chromophore in solution. In contrast to the commonly used low intensity technique that depends on the quadratic-intensity law, the present technique is based on the non-quadratic-intensity dependence of two-photon fluorescence. Auxiliary data such as two-photon quantum efficiency and fluorescence collection efficiency, essential in the low intensity method, are not required in the present technique. TPF measurements of Rhodamine B in methanol are carried out to demonstrate the validity of the present method. The method is used to determine the two-photon absorption cross section of a new chromophore attached with tricyano-derivatized furan as the electron acceptor. The two-photon absorption cross section measured using this method is also compared with that using a conventional transmission technique.     

The absorption spectrum of water near 750 nm by CW-CRDS: contribution to the search of water dimer absorption

The absorption spectrum of natural water vapour around 750 nm has been recorded with a typical sensitivity of 3 x 10(-10) cm(-1) using a cw cavity ring down spectroscopy set up based on a Ti:sapphire laser. The 13 312.4-13 377.7 cm(-1) spectral interval was chosen as it corresponds to the region where water dimer absorption was recently measured (K. Pfeisticker et al., Science, 2003, 300, 2078-2080). The line parameters (wavenumber and intensity) of a total of 286 lines of water vapor were measured by a one by one fit of the lines to a Voigt profile. For the main water isotopologue, 276 lines were measured with line intensities as weak as 5 x 10(-29) cm molecule(-1)i.e. about 50 times smaller than the weakest H(2)16O line intensities included in the 2004 edition of the HITRAN database. On the basis of the predictions of Schwenke and Partridge, all but 16 lines could be assigned to different isotopologues of water (H(2)16O, H(2)18O, and HD16O) present in natural abundance in the sample. A total of 272 energy levels of H(2)16O were determined and rovibrationally assigned to 18 upper vibrational states. Half of them had not been reported previously. The importance of the additional absorbance resulting from the observation of many new weak lines is discussed in relation to the detection of water dimer absorption and compared to the absorbance predicted by Schwenke and Partridge. The quality of the line parameters of water monomer is shown to be of crucial importance to identify the absorbance of the water dimer in the considered region.     

Discharge-flow kinetics measurements using intracavity laser absorption spectroscopy

Intracavity laser absorption spectroscopy ("ICLAS") has been demonstrated as a feasible detection method for trace species in a discharge flow tube. This implementation has been used to measure the rate of the reaction between atomic hydrogen and NO to form HNO in helium carrier gas. A reaction rate constant of (4.3 +/- 0.4) x 10(-32) cm(6) molecule(-2) s(-1) at 295 K was measured for the reaction H + NO + M --> HNO + M (M = He). The pressure and concentration range enabled by ICLAS detection has allowed us to limit reactive pathways that would inhibit the formation of HNO. The sensitivity of ICLAS, coupled with the versatility of the discharge flow technique, suggests that intracavity absorption spectroscopy will be a useful technique for kinetics measurements on free radicals and other reactive species.     

Energy transfer and amplified spontaneous emission in temperature-controlled random scattering media

Hydroxypropyl cellulose (HPC) in aqueous solution forms nanoparticles and becomes highly scattering above its lower critical solution temperature (LCST approximately 41 degrees C). Enhancement of energy transfer (ET) and amplified spontaneous emission (ASE) have been observed in turbid HPC solutions containing Rhodamine 6G (RG) as an energy donor and Kiton Red 620 (KR) as an acceptor. A detailed analysis of self-absorption, absorption saturation, and multiple scattering effects has revealed the importance of photon diffusion in shutting down the intensity leakage. A 5-fold enhancement of ET in the turbid condition is estimated. Possible factors crucial for ET and ASE in random media are discussed, such as the donor-to-acceptor ASE energy pumping, the optical path elongation by multiple scattering, and the formation of "light pipes" in the near-field of the Mie scattering. The temperature-dependent colloidal formation is found to successfully control optical processes via multiple scattering with a sharp threshold and abrupt emergence of dense scatterers.     

CH radical production from 248 nm photolysis or discharge-jet dissociation of CHBr3 probed by cavity ring-down absorption spectroscopy

The A-X bands of the CH radical, produced in a 248 nm two-photon photolysis or in a supersonic jet discharge of CHBr(3), have been observed via cavity ring-down absorption spectroscopy. Bromoform is a well-known photolytic source of CH radicals, though no quantitative measurement of the CH production efficiency has yet been reported. The aim of the present work is to quantify the CH production from both photolysis and discharge of CHBr(3). In the case of photolysis, the range of pressure and laser fluences was carefully chosen to avoid postphotolysis reactions with the highly reactive CH radical. The CH production efficiency at 248 nm has been measured to be Phi=N(CH)N(CHBr(3))=(5.0+/-2.5)10(-4) for a photolysis laser fluence of 44 mJ cm(-2) per pulse corresponding to a two-photon process only. In addition, the internal energy distribution of CH(X (2)Pi) has been obtained, and thermalized population distributions have been simulated, leading to an average vibrational temperature T(vib)=1800+/-50 K and a rotational temperature T(rot)=300+/-20 K. An alternative technique for producing the CH radical has been tested using discharge-induced dissociation of CHBr(3) in a supersonic expansion. The CH product was analyzed using the same cavity ring-down spectroscopy setup. The production of CH by discharge appears to be as efficient as the photolysis technique and leads to rotationally relaxed radicals.     

Laser intensity effects in the IR multiple-photon absorption of OsO4

The visible luminescence resulting from multiple-photon absorption of CO₂ laser radiation in OsO₄ depends upon the laser intensity as well as fluence. The use of single-mode laser pulses, shaped by electro-optic crystal switching, has enabled this intensity dependence to be determined quantitatively.     

Atomic absorption with ultracold atoms

Recent advances in laser-atom cooling techniques and diode-laser technology now allow one to conduct an idealised atomic absorption experiment comprising a sample of ultracold, quasi-stationary absorbing atoms and a source of near-monochromatic resonant light. Under such conditions, the atomic absorption coefficient at line centre is independent of the oscillator strength of the atomic resonance line. This offers the prospect of ‘oscillator-strength-free’ atomic absorption spectroscopy in which the absorption signal is equally large for both strong and weak (closed) transitions of the same wavelength and in which absolute atomic absorption could be performed without knowledge of the oscillator strength. Moreover, the resolution and sensitivity for a given atom density are greatly enhanced, typically by approximately three orders of magnitude (and even more for weak transitions), compared with conventional flame or graphite-furnace atomic absorption. We describe an atomic absorption experiment based on samples of ultracold, laser-cooled caesium atoms and a narrow-bandwidth diode laser source that approximates the idealised conditions for oscillator-strength-free atomic absorption. The absorption measurements are used to determine the number density and temperature (approx. 6 μK) of the sample of ultracold atoms. Some of the technical obstacles that would have to be overcome before samples of ultracold atoms and diode laser sources could be used in analytical atomic absorption spectroscopy are discussed.     

Cavity ringdown spectroscopy: broad band absolute absorption measurements

Here we report further results in our recent extension of cavity ring down spectroscopy (CRDS) to CW single frequency lasers. We previously pointed out the excellent reproducibility of our spectra, in particular the baseline measurements obtained from the empty cavity. The ability of accurately measuring the zero absorption baseline is essential when studying very broad or congested absorption spectra or even continua. We demonstrate the performance of our CW-CRDS setup by obtaining the absolute absorption spectrum of a weak and broad overtone transition in CHF₃. We also discuss how the present results will apply to conventional pulsed-CRDS.     

基于DFB型半导体激光器的腔增强吸收光谱研究

The Cavity enhanced absorption spectroscopy based on a tunable DFB diode laser (TDL-CEAS) was described. A brief introduction of cavity enhanced absorption spectroscopy development and experimental scheme was given, the effective absorption path of the medium in the optical cavity was interpreted from the way of Fabry Perot cavity. It is pointed out that the main reason why CEAS has high detection sensitivity is that the medium in the cavity can get a long absorption path. A tunable DFB diode laser which center wavelength is 1.573 μm was used as the light source, and an optical cavity which consists of two high reflectivity mirrors (near 1.573 μm, R about 0.994) separated at a distance of 34 cm was used as the absorption cell. Laser radiation was coupled into the optical cavity via accidental coincidences of laser frequency with the cavity mode when scanning the cavity and the laser. An absorption spectrum of carbon dioxide near 1.573 μm was obtained and a detection sensitivity of about 1.66×10-5 cm-1 was achieved. It is experimentally demonstrated that the CEAS is a highly sensitive and high resolution spectrum technology, and it has the advantage of simple experimental setup and easy operation.