In this experiment, the thermal lens technique is used with a modified arrangement of three lasers to induce a two‐color absorption. Two‐pump lasers, a variable wavelength orange dye laser (588–617 nm), a single line blue laser (488 nm), and a single line probe yellow laser (568 nm) are employed. A comparison is made between the magnitude of the thermal lens signal obtained with a one pump laser versus two pump lasers. The absorbing molecules are benzene and naphthalene in liquid n‐Hexane. The CH vibrational overtone spectra are obtained at room temperature for several concentrations. The molecules are excited to a high vibrational state (Δυ = 6) with the first laser and to an electronic level with a second laser (two‐color absorption). Using two pump lasers, the limit of detection of the molecule is several orders of magnitude more sensitive than using one pump laser. A nonlinear behavior of the integrated signal versus concentration is shown for the two‐color laser process. Linear behavior is shown for the one pump laser experiment. A model of signal amplification for a nonlinear absorption is presented to explain the results. The separation and identification of CH overtone bands in molecules and the sensitivity of the technique is emphasized to convey the potential use of CH overtone spectroscopy for imaging in thermal lens microscopy.

No abstract

The thermal lens technique is applied to vibrational overtone spectroscopy of solutions of naphthalene (CH) in liquid hexane. The C-H fifth vibrational (Δν = 6) overtone spectrum of CH is detected at room temperature for mole fractions from 0.08 to 19 × 10 using n-CH as solvent. By detecting the absorption band in a 19 ppm (parts per million) solution, the peak absorption of the signal is approximately (2.2 ± 0.3) × 10cm. A plot of normalized integrated intensity as a function of the mole fraction of naphthalene in solution reveals a dependence of the magnitude of the signal with the probe laser wavelength. If the wavelength of the probe laser is 568 nm, the thermal lens signal (TLS) is linear as a function of the mole fraction of the solution. When the wavelength of the probe laser is 488 nm, the TLS is nonlinear as a function of the concentration. Three different models of nonlinear absorption are discussed. A two-color absorption model that includes the simultaneous absorption of the pump and probe lasers could explain the enhanced magnitude and the nonlinear behavior of the TLS for solutions of mole fraction < 0.1%.

The thermal lens technique is applied to vibrational overtone spectroscopy of solutions of naphthalene in n-hexane. The pump and probe thermal lens technique is found to be very sensitive for detecting samples of low composition (ppm) in transparent solvents. In this experiment two different probe lasers: one at 488 nm and another 568 nm were used. The C-H fifth vibrational overtone spectrum of benzene is detected at room temperature for different concentrations. A plot of normalized integrated intensity as a function of concentration of naphthalene in solution reveals a non-linear behavior at low concentrations when using the 488 nm probe and a linear behavior over the entire range of concentrations when using the 568 nm probe. The non-linearity cannot be explained assuming solvent enhancement at low concentrations. A two color absorption model that includes the simultaneous absorption of the pump and probe lasers could explain the enhanced magnitude and the non-linear behavior of the thermal lens signal. Other possible mechanisms will also be discussed.