Electronic-resonance-enhanced Coherent anti-Stokes Raman Scattering Research Articles

Concentration and pressure scaling of CH2O electronic-resonance-enhanced coherent anti-Stokes Raman scattering signals.

Nanosecond electronic-resonance-enhanced coherent anti-Stokes Raman scattering (ERE-CARS) is evaluated for the measurement of formaldehyde (CH2O) concentrations in reacting and nonreacting conditions. The three-color scheme utilizes a 532 nm pump beam and a scanned Stokes beam near 624 nm for Raman excitation of the C-H symmetric stretch (ν1) vibrational mode; further, a 342 nm resonant probe is tuned to produce the outgoing CARS signal via the 101403 vibronic transition between the ground (X~1A1) and first excited (A~1A2) electronic states. This allows detection of CH2O at concentrations as low as 9×1014molecules/cm3 (55 parts per million) in a calibration cell with CH2O and N2 at 1 bar and 450 K with 3% uncertainty. The measurements show a quadratic dependence of the signal with CH2O number density. Pressure scaling experiments up to 11 bar in the calibration cell show an increase in signal up to 8 bar. We study pressure dependence up to 11 bar and further apply the technique to characterize the CH2O concentration in an atmospheric premixed dimethyl ether/air McKenna burner flame, with a maximum concentration uncertainty of 11%. This approach demonstrates the feasibility for spatially resolved measurements of minor species such as CH2O in reactive environments and shows promise for application in high-pressure combustors.

Femtosecond time-resolved ERE-CARS of PM650

We utilize femtosecond time-resolved electronic resonance-enhanced coherent anti-Stokes Raman scattering (ERE-CARS) to investigate new information for pyrromethene 650 (PM650) dye molecules. For this purpose, the vibrational properties of PM650 are registered in diluted solutions of several organisms. We observe a strong Raman vibrational mode with a wavenumber difference of about 48cm−1 in its organic solutions. This may be linked to the intramolecular electron transfer (ICT) process from the aromatic ring to the cyano group in PM650. The influence of the solvent effects on the vibrational dynamics of PM650 is also investigated. The vibrational properties of PM650 dye molecules diluted in polar organic solutions are light solvent-dependent.

Femtosecond Time-Resolved ERE-CARS of CV670 Dye in Solutions

We utilize femtosecond time-resolved electronic resonance-enhanced coherent anti-Stokes Raman scattering (ERE-CARS) to study the vibrational dynamics of cresyl violet 670 (CV670) dye molecules. For this purpose, the vibrational properties of CV670 are registered in diluted solutions of ethanol and methanol. By changing the timing (Δt > 0) of the laser pulses of this nondegenerate four wave mixing technique, the wavepacket dynamics on the electronically ground state can be detected as oscillations in the ERE-CARS signal. Two strong Raman vibrational modes with an average period of 0.401 and 0.423 ps in CV670–ethanol solutions are obtained simultaneously, and we observe a qualitative vibrational dephasing time difference of the Raman vibrational modes of CV670 in ethanol and methanol solvents (5 × 10–5 mol/L), which may be due to the influence of the formation of the supramolecular structures in CV670–ethanol and CV670–methanol mixtures on the Raman modes of CV670.

Effects of collisions on electronic-resonance-enhanced coherent anti-Stokes Raman scattering of nitric oxide

A six-level model is developed and used to study the effects of collisional energy transfer and dephasing on electronic-resonance-enhanced coherent anti-Stokes Raman scattering (ERE-CARS) in nitric oxide. The model includes the three levels that are coherently coupled by the three applied lasers as well as three additional bath levels that enable inclusion of the effects of electronic quenching and rotational energy transfer. The density-matrix equations that describe the evolution of the relevant populations and coherences are presented. The parametric dependencies of the ERE-CARS signal on collisional energy transfer and dephasing processes are described in terms of both a steady-state analytical solution and the numerical solutions to the governing equations. In the weak-field limit, the ERE-CARS signal scales inversely with the square of the dephasing rates for the electronic and Raman coherences. In accord with published experimental observations [Roy et al., Appl. Phys. Lett. 89, 104105 (2006)], the ERE-CARS signal is shown to be insensitive to the collisional quenching rate. Parametric dependencies on quenching, rotational energy transfer, and pure electronic dephasing are presented, demonstrating reduced collisional dependence for saturating laser fields.

Collisional effects on molecular dynamics in electronic-resonance-enhanced CARS

The role of collisional decay on the evolution of molecular coherence and excited-state population in an electronic-resonance-enhanced coherent anti-Stokes Raman scattering (ERE-CARS) configuration is studied. A four-level model scheme is proposed and a density-matrix equation is derived to determine the system evolution. It is shown that even for significantly large collisional decays, a suitable (rather strong) probe-laser intensity prevents significant depletion of the excited-state population and enhances the ground-state coherence. A physical understanding is developed for the reported insensitivity [Roy et al. Appl. Phys. Lett. 2006, 89, 104105] of the ERE-CARS signal to the rate of collisional decay at the excited electronic level.

Single-laser-shot detection of nitric oxide in reacting flows using electronic resonance enhanced coherent anti-Stokes Raman scattering

Single-laser-shot electronic resonance enhanced coherent anti-Stokes Raman scattering (ERE-CARS) spectra of nitric oxide (NO) were generated using the 532 nm output of an injection-seeded Nd:YAG (yttrium aluminum garnet) laser as the pump beam, a broadband dye laser at approximately 591 nm as the Stokes beam, and a 236 nm narrowband ultraviolet probe beam. Single-laser-shot ERE-CARS spectra of NO were acquired in an atmospheric-pressure hydrogen/air counterflow diffusion flame. The single-shot detection limit in this flame was found to be approximately 30 ppm, and the standard deviation of the measured NO concentration was found to be approximately 20% of the mean.

Nitric oxide concentration measurements in atmospheric pressure flames using electronic-resonance-enhanced coherent anti-Stokes Raman scattering

We report the application of electronic-resonance-enhanced coherent anti-Stokes Raman scattering (ERE-CARS) for measurements of nitric oxide concentration ([NO]) in three different atmospheric pressure flames. Visible pump (532 nm) and Stokes (591 nm) beams are used to probe the Q-branch of the Raman transition. A significant resonance enhancement is obtained by tuning an ultraviolet probe beam (236 nm) into resonance with specific rotational transitions in the (v’=0, v”=1) vibrational band of the A2Σ+–X2Π electronic system of NO. ERE-CARS spectra are recorded at various heights within a hydrogen-air flame producing relatively low concentrations of NO over a Hencken burner. Good agreement is obtained between NO ERE-CARS measurements and the results of flame computations using UNICORN, a two-dimensional flame code. Excellent agreement between measured and calculated NO spectra is also obtained when using a modified version of the Sandia CARSFT code for heavily sooting acetylene-air flames (φ=0.8 to φ=1.6) on the same Hencken burner. Finally, NO concentration profiles are measured using ERE-CARS in a laminar, counter-flow, non-premixed hydrogen-air flame. Spectral scans are recorded by probing the Q1 (9.5), Q1 (13.5) and Q1 (17.5) Raman transitions. The measured shape of the [NO] profile is in good agreement with that predicted using the OPPDIF code, even without correcting for collisional effects. These comparisons between [NO] measurements and predictions establish the utility of ERE-CARS for detection of NO in flames with large temperature and concentration gradients as well as in sooting environments.

Detection of acetylene by electronic resonance-enhanced coherent anti-Stokes Raman scattering

We report the detection of acetylene (C2H2) at low concentrations by electronic resonance-enhanced coherent anti-Stokes Raman scattering (ERE-CARS). Visible pump and Stokes beams are tuned into resonance with Q-branch transitions in the v2 Raman band of acetylene. An ultraviolet probe beam is tuned into resonance with the $\tilde{A}$ – $\tilde{X}$ electronic transition of C2H2, resulting in significant electronic resonance enhancement of the CARS signal. The signal is found to increase significantly with rising pressure for the pressure range 0.1–8 bar at 300 K. Collisional narrowing of the spectra appears to be important at 2 bar and above. A detection limit of approximately 25 ppm at 300 K and 1 bar is achieved for our experimental conditions. The signal magnitudes and the shape of the C2H2 spectrum are essentially constant for UV probe wavelengths from 233.0 to 238.5 nm, thus indicating that significant resonant enhancement is achieved even without tuning the probe beam into resonance with a specific electronic resonance transition.

Effects of pressure variations on electronic-resonance-enhanced coherent anti-Stokes Raman scattering of nitric oxide

The effects of pressure variations on the electronic-resonance-enhanced coherent anti-Stokes Raman scattering (ERE-CARS) signal of nitric oxide (NO) were studied at pressures ranging from 0.1 to 8 bar. ERE-CARS signals were recorded in a gas cell filled with a mixture of 300 ppm NO in N 2 buffer gas at room temperature. The ERE-CARS signal was found to increase with rising pressure up to 2 bar and to remain nearly constant thereafter. The spectra recorded at different cell pressures were modeled using a modified version of the Sandia CARSFT code. Laser-saturation effects were accounted for by systematically varying the theoretical ultraviolet probe-laser linewidth. Excellent agreement was obtained between theory and experiment for the pressure-scaling behavior of the ERE-CARS signal of NO. This finding, along with a negligible influence of electronic quenching on the ERE-CARS signal, provides strong incentive for the application of ERE-CARS to measurements of NO concentrations in high-pressure combustion environments.

Effects of quenching on electronic-resonance-enhanced coherent anti-Stokes Raman scattering of nitric oxide

We investigate the effects of gas-mixture composition on the electronic-resonance-enhanced coherent anti-Stokes Raman scattering (ERE-CARS) signals of nitric oxide (NO). From previous laser-induced fluorescence (LIF) studies, quenching rates are known to change drastically, by factors of 400–800, in mixtures of CO2∕O2∕N2. The observed ERE-CARS signal remains constant to within 30% whereas LIF signals from NO are predicted to decrease by more than two orders of magnitudes in the same environments. This is very significant for using NO ERE-CARS in high-pressure combustion environments where the electronic quenching rate can vary rapidly as a function of both space and time.