Nonperturbative modeling of two-photon absorption in a three-state system

The physics of the two-photon absorption process is investigated for a three-state system. The density-matrix equations for the two-photon interaction are solved in the steady-state limit assuming that the pump laser radiation is monochromatic. Collisional broadening, saturation, and Stark shifting of the two-photon resonance are investigated in detail by numerical solution of the steady-state density-matrix equations. Analytical expressions for the saturation intensity and the Stark shift are derived for the case where the single-photon transitions between the intermediate state and the initial and final states are far from resonance with the pump laser. For this case, it is found that the direction of the Stark shift is dependent on the relative magnitudes of the dipole-moment matrix elements for the single-photon transitions that couple the intermediate state with the initial and final states. Saturation and Stark shifting are also investigated for the case where the single-photon transitions between the intermediate state and the initial and final states are close to resonance with the pump laser.     

10 kHz detection of CO2 at 4.5 microm by using tunable diode-laser-based difference-frequency generation

A compact, high-speed tunable, diode-laser-based mid-infrared (MIR) laser source has been developed for absorption spectroscopy of CO2 at rates up to 10 kHz. Radiation at 4.5 microm with a mode-hop-free tuning range of 80 GHz is generated by difference-frequency mixing the 860 nm output of a distributed-feedback diode laser with the 1064 nm output of a diode-pumped Nd:YAG laser in a periodically poled lithium niobate crystal. MIR absorption spectroscopy of CO2 with a detection limit of 44 ppm m at 10 kHz is demonstrated in a C2H4-air laminar diffusion flame and in the exhaust of a liquid-fueled model gas-turbine combustor.     

Theory of femtosecond coherent anti-Stokes Raman scattering spectroscopy of gas-phase transitions

A theoretical analysis of coherent anti-Stokes Raman scattering (CARS) spectroscopy of gas-phase resonances using femtosecond lasers is performed. The time-dependent density matrix equations for the femtosecond CARS process are formulated and manipulated into a form suitable for solution by direct numerical integration (DNI). The temporal shapes of the pump, Stokes, and probe laser pulses are specified as an input to the DNI calculations. It is assumed that the laser pulse shapes are 70 fs Gaussians and that the pulses are Fourier-transform limited. A single excited electronic level is defined as an effective intermediate level in the Raman process, and transition strengths are adjusted to match the experimental Raman polarizability. The excitation of the Raman coherence is investigated for different Q-branch rotational transitions in the fundamental 2330 cm(-1) band of diatomic nitrogen, assuming that the pump and Stokes pulses are temporally overlapped. The excitation process is shown to be virtually identical for transitions ranging from Q2 to Q20. The excitation of the Raman coherences is also very efficient; for laser irradiances of 5x10(17) W/m2, corresponding approximately to a 100 microJ, 70 fs pulse focused to 50 microm, approximately 10% of the population of the ground Raman level is pumped to the excited Raman level during the impulsive pump-Stokes excitation, and the magnitude of the induced Raman coherence reaches 40% of its maximum possible value. The theoretical results are compared with the results of experiments where the femtosecond CARS signal is recorded as a function of probe delay with respect to the impulsive pump-Stokes excitation.     

Femtosecond two-photon LIF imaging of atomic species using a frequency-quadrupled Ti:sapphire laser

Femtosecond (fs)-duration laser pulses are well suited for two-photon laser-induced-fluorescence (TPLIF) imaging of key atomic species such as H, N, and O in gas-phase reacting flows. Ultrashort pulses enable efficient nonlinear excitation, while reducing interfering photochemical processes. Furthermore, amplified fs lasers enable high-repetition-rate imaging (typically 1–10 kHz) for capturing the dynamics of turbulent flow fields. However, two-dimensional (2D), single-laser-shot fs-TPLIF imaging of the above species is challenging in most practical flow fields because of the limited ultraviolet pulse energy available in commercial optical parametric amplifier (OPA)-based tunable laser sources. In this work, we report the development of an efficient, fs frequency-quadrupling unit [i.e., fourth-harmonic generator (FHG)] with overall conversion efficiency more than six times greater than that of commercial OPA-based systems. The development, characterization, and application of the fs-FHG system for 2D imaging of H atoms in flames are described in detail. The potential application of the same laser system for 2D imaging of N and O atoms is also discussed.     

Molybdenum(VI) complexes of a 2,2'-biphenyl-bridged bis(amidophenoxide): competition between metal-ligand and metal-amidophenoxide π bonding

The 2,2'-biphenyl-bridged bis(2-aminophenol) ligand 4,4'-di-tert-butyl-N,N'-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-2,2'-diaminobiphenyl ((t)BuClipH(4)) reacts with MoO(2)(acac)(2) to form ((t)BuClipH(2))MoO(2), where the diarylamines remain protonated and bind trans to the terminal oxo groups. This complex readily loses water on treatment with pyridine or 3,5-lutidine to form mono-oxo complexes ((t)BuClip)MoO(L), which exhibit predominantly a cis-β geometry with an aryloxide trans to the oxo group. Exchange of the pyridine ligands is rapid and takes place by a dissociative mechanism, which occurs with retention of stereochemistry at molybdenum. Oxo-free alkoxide complexes ((t)BuClip)Mo(OR)(2) are formed from ((t)BuClipH(2))MoO(2) and ROH. Treatment of NMo(O(t)Bu)(3) with (t)BuClipH(4) results in complete deprotonation of the bis(aminophenol) and formation of a dimolybdenum complex ((t)BuClip)Mo(μ-N)(μ-NH(2))Mo((t)BuClip) containing both a bridging nitride (Mo-N = 1.848 ?, Mo-N-Mo = 109.49°) and a bridging amide group. The strong π bonding of this bis(amidophenoxide) ligand allows the molybdenum center to interconvert readily among species forming three, two, one, or zero π bonds from multiply bonded ligands.     

Investigation of optical fibers for coherent anti-Stokes Raman scattering (CARS) spectroscopy in reacting flows

The objective of this work is to investigate the feasibility of intense laser-beam propagation through optical fibers for temperature and species concentration measurements in gas-phase reacting flows using coherent anti-Stokes Raman scattering (CARS) spectroscopy. In particular, damage thresholds of fibers, nonlinear effects during beam propagation, and beam quality at the output of the fibers are studied for the propagation of nanosecond (ns) and picosecond (ps) laser beams. It is observed that ps pulses are better suited for fiber-based nonlinear optical spectroscopic techniques, which generally depend on laser irradiance rather than fluence. A ps fiber-coupled CARS system using multimode step-index fibers is developed. Temperature measurements using this system are demonstrated in an atmospheric pressure, near-adiabatic laboratory flame. Proof-of-concept measurements show significant promise for fiber-based CARS spectroscopy in harsh combustion environments. Furthermore, since ps-CARS spectroscopy allows the suppression of non-resonant background, this technique could be utilized for improving the sensitivity and accuracy of CARS thermometry in high-pressure hydrocarbon-fueled combustors.     

Single‐beam coherent anti‐Stokes Raman scattering (CARS) spectroscopy of gas‐phase CO2 via phase and polarization shaping of a broadband continuum

Coherent anti‐Stokes Raman scattering (CARS) spectroscopy of gas‐phase CO₂ is demonstrated using a single femtosecond (fs) laser beam. A shaped ultrashort laser pulse with a transform‐limited temporal width of ∼7 fs and spectral bandwidth of ∼225 nm (∼3500 cm⁻¹) is employed for simultaneous excitation of the CO₂ Fermi dyads at ∼1285 and ∼1388 cm⁻¹. CARS signal intensities for the two Raman transitions and their ratio as a function of pressure are presented. The signal‐to‐noise ratio of the single beam–generated CO₂ CARS signal is sufficient to perform concentration measurements at a rate of 1 kHz. The implications of these experiments for measuring CO₂ concentrations and rapid pressure fluctuations in hypersonic and detonation‐based chemically reacting flows are also discussed. Copyright © 2010 John Wiley & Sons, Ltd.     

Diode-laser-based ultraviolet-absorption sensor for high-speed detection of the hydroxyl radical

A new diode-laser-based UV-absorption sensor for high-speed detection of the hydroxyl radical (OH) is described. The sensor is based on sum-frequency generation of UV radiation at 313.5 nm by mixing the output of a 763-nm distributed-feedback diode laser with that of a 532-nm high-power, diode-pumped, frequency-doubled Nd:YVO4 laser in a beta-barium borate crystal. Approximately 25 microW of UV radiation is generated and used to probe rotational transitions in the A2 Sigma+ -X2II (v' = 0, v" = 0) electronic transition of OH. Single-sweep, single-pass measurements of temperature and OH concentration in a stoichiometric C2H4-air flame are demonstrated at rates up to 20 kHz.