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.
Saturation effects in coherent anti-Stokes Raman scattering (CARS) spectroscopy are discussed. The discussion is limited to Raman-resonant CARS (${\ensuremath{\omega}}_{l}\ensuremath{-}{\ensuremath{\omega}}_{s}\ensuremath{\simeq}{\ensuremath{\omega}}_{21}$, where ${\ensuremath{\omega}}_{l,s}$ are the frequencies of the pump fields with powers
Pl,s, and ${\ensuremath{\omega}}_{21}$ is the frequency of the Raman transition $|1〉\ensuremath{\rightarrow}|2〉$) with the possible addition of a one-photon resonance (${\ensuremath{\omega}}_{l}\ensuremath{\simeq}{\ensuremath{\omega}}_{31}$ is the frequency of the electronic transition $|1〉\ensuremath{\rightarrow}|3〉$). For these cases we show that the CARS polarization
pCARS is proportional to the off-diagonal density-matrix element ${\ensuremath{\rho}}_{21}$. In order to determine ${\ensuremath{\rho}}_{21}$, we use Laplace transforms to solve the Bloch equations for the effective two-level system
∣1〉 and
∣2〉 when ${\ensuremath{\omega}}_{l}$ is far from resonance, or for the three-level system
∣1〉,∣2〉, and
∣3〉, when ${\ensuremath{\omega}}_{l}\ensuremath{\simeq}{\ensuremath{\omega}}_{31}$. The steady-state expression for
pCARS in the former case gives ${\mathcal{p}}_{\mathrm{CARS}}\ensuremath{\propto}{P}_{l}{P}_{s}^{\frac{1}{2}}$ at low powers and ${\mathcal{p}}_{\mathrm{CARS}}\ensuremath{\propto}{P}_{l}^{0}{P}_{s}^{\frac{\ensuremath{-}1}{2}}$ at high powers. In the three-level system, we show that when the pressure is low and at least one field is weak, the slow time dependence of ${\ensuremath{\rho}}_{21}$ must be considered. When one field is strong and the other weak, the CARS spectrum is Stark split. When
Pl is high, for example, ${\mathcal{p}}_{\mathrm{CARS}}\ensuremath{\propto}{P}_{l}^{0}{P}_{s}^{\frac{1}{2}}$ for ${\ensuremath{\omega}}_{s}\ensuremath{\simeq}{\ensuremath{\omega}}_{32}$ and ${\mathcal{p}}_{\mathrm{CARS}}\ensuremath{\propto}{({P}_{l}{P}_{s})}^{\frac{1}{2}}$ when ${\ensuremath{\omega}}_{s}\ensuremath{\simeq}{\ensuremath{\omega}}_{32}\ifmmode\pm\else\textpm\fi{}{V}_{13}$ where
V13 is the one-photon Rabi frequency for the $|1〉\ensuremath{\rightarrow}|3〉$ transition. The Wilcox-Lamb approximation is used to reduce the three-level Bloch equations to rate equations containing one- and two-photon terms. When the fields are so weak that both one- and two-photon terms are small compared to the decay terms, the usual expression for
pCARS is reproduced. If only the direct two-photon processes are important, the effective-two-system results are reproduced. When both fields are intense and nearly resonant, the steady state is rapidly achieved. The results for the case where one field is much stronger than the other are essentially the same as those for one strong and one weak field. When the fields are of comparable strength, ${\mathcal{p}}_{\mathrm{CARS}}\ensuremath{\propto}{P}_{l}^{\frac{1}{2}}{P}_{s}^{0}$ for ${\ensuremath{\omega}}_{l}\ensuremath{\simeq}{\ensuremath{\omega}}_{31}$ and ${\ensuremath{\omega}}_{s}\ensuremath{\simeq}{\ensuremath{\omega}}_{32}$, and the CARS spectrum is split into five components.
The saturation threshold of a probe pulse in an ultrafast electronic-resonance-enhanced (ERE) coherent anti-Stokes Raman spectroscopy (CARS) configuration is calculated. We demonstrate that while the underdamping condition is a sufficient condition for saturation of ERE-CARS with the long-pulse excitations, a transient gain must be achieved to saturate the ERE-CARS signal for the ultrafast probe regime. We identify that the area under the probe pulse can be used as a definitive parameter to determine the criterion for a saturation threshold for ultrafast ERE-CARS. From a simplified analytical solution and a detailed numerical calculation based on density-matrix equations, the saturation threshold of ERE-CARS is compared for a wide range of probe-pulse durations from the 10-ns to the 10-fs regime. The theory explains both qualitatively and quantitatively the saturation thresholds of resonant transitions and also gives a predictive capability for other pulse duration regimes. The presented criterion for the saturation threshold will be useful in establishing the design parameters for ultrafast ERE-CARS.
The theory of coherent anti-Stokes Raman scattering (CARS) is extended to include the effect of pump fluctuations. The intensities and spectra of lines in resonant CARS are calculated to all orders in fields assuming a phase-diffusion model for waves at the two pump frequencies. The bandwidth of the two lasers enters in a much more complicated way than following a simple scaling of
T1 or
T2. Various resonances in CARS spectra due to dynamic splitting of the energy levels are discussed for a range of detunings, field intensities, and bandwidths. In contrast to the usual spectra in strong fields, the Rabi sidebands appear as dispersion-shaped structures. The laser linewidth is shown to change dramatically the CARS line shape. The case of no saturation is also treated, thus allowing for the inclusion of more general line shapes and fluctuations of the pump waves and the nonlinear susceptibility tensor ${\ensuremath{\chi}}^{(3)}$. Gaussian statistics of the pump field are shown to lead to enhancement factors in CARS intensity, similar to those appearing in the context of multiphoton absorption processes.
Resonance-enhanced four-wave-mixing processes were studied in molecular iodine by detection of a wave generated at frequency ${\mathrm{\ensuremath{\omega}}}_{3}$=2${\mathrm{\ensuremath{\omega}}}_{1}$-${\mathrm{\ensuremath{\omega}}}_{2}$ for a wide range of Raman frequencies (${\mathrm{\ensuremath{\omega}}}_{1}$-${\mathrm{\ensuremath{\omega}}}_{2}$). On the basis of known spectroscopic constants of the two electronic states involved, the electronic ground state
X1${\mathrm{\ensuremath{\Sigma}}}_{\mathit{g}}^{+}$ and the electronic excited state
B3${\mathrm{\ensuremath{\Pi}}}_{\mathit{u}0}^{+}$, an interpretation of the spectral features in terms of three essentially different four-wave-mixing processes is given. Resonance enhancement through bound states with discrete energy levels and the enhancement effect by dissociative continuum states are considered. In addition to resonance-enhanced coherent anti-Stokes Raman-scattering (CARS) processes, in which the Raman resonances are in the electronic ground state, two resonant schemes are identified in
I2, in which Raman resonances in an excited state are probed: excited-state parametric and nonparametric CARS. The latter process is an example of electronic population transfer in a four-wave-mixing cycle.
A semiclassical theory that describes the generation of a coherent anti-Stokes Raman scattering (CARS) signal is presented that maximizes vibrational coherence in a mode predetermined by the pump, the Stokes, and the probe chirped pulse trains and takes into account the field propagation effects in a cloud of molecules. The buildup of the anti-Stokes signal, which may be used as a molecular signature in the backward CARS signal, is demonstrated numerically. The theory is based on the solution of the coupled Maxwell's and Liouville--von Neumann equations and focuses on the quantum effects induced in the target molecules by the control pulse trains. A deep convolutional neural network technique is implemented to evaluate time-dependent phase characteristics of the control fields. The effect of decoherence induced by spontaneous decay and collisional dephasing is examined.