Coherent Raman scattering spectroscopy and microscopy are useful methods for studying the chemical and biological structures of molecules with Raman-active modes. In particular, coherent anti-Stokes Raman scattering (CARS) microscopy, which is a label-free method capable of imaging structures by displaying the vibrational contrast of the molecules, has been widely used. However, the lack of a technique for switching-off the CARS signal has prevented the development of the super-resolution Raman imaging method. Here, we demonstrate that a selective suppression of the CARS signal is possible by using a three-beam double stimulated Raman scattering (SRS) scheme; the three beams are the pump, Stokes, and depletion lights in order of frequency. Both pump-Stokes and pump-depletion beam pairs can generate SRS processes by tuning their beat frequencies to match two different vibrational modes, then two CARS signals induced by pump-Stokes-pump and pump-depletion-pump interactions can be generated, where the two CARS signals are coupled with each other because they both involve interactions with the common pump beam. Herein, we show that as the intensity of the depletion beam is increased, one can selectively suppress the pump-Stokes-pump CARS signal because the pump-depletion SRS depletes the pump photons. A detailed theoretical description of the coupled differential equations for the three incident fields and the generated CARS signal fields is presented. Taking benzene as a molecular system, we obtained a maximum CARS suppression efficiency of about 97% with our experimental scheme, where the ring breathing mode of the benzene is associated with pump-Stokes-pump CARS, while the C-H stretching mode is associated with the competing pump-depletion SRS process. We anticipate that this selective switching-off scheme will be of use in developing super-resolution label-free CARS microscopy.
Motivated by recent efforts to achieve sub-femtosecond structural resolution in various molecular systems, we have performed a femtosecond quantum dynamics study of the water cation in the X ̃(2)B1 and Ã(2)A1 electronic states. Autocorrelation functions for H2O(+) and D2O(+) are calculated for such electronic states by solving numerically the time-dependent Schrödinger equation. From the ratio of the squared autocorrelation functions of D2O(+) and H2O(+), the high-order harmonic generation signals are calculated. Substantial vibrational dynamics is found in the Ã(2)A1 state as compared to the one in X ̃(2)B1, which supports recent experimental findings of Farrell et al., Phys. Rev. Lett., 2011, 107, 083001. Maxima in the above ratio are also predicted at ∼1.1 fs and ∼1.6 fs for the X ̃(2)B1 and Ã(2)A1 states, respectively. The expectation values of the positions of the atoms in H2O(+) as a function of time reveal a strong excitation of the bending mode in the Ã(2)A1 state, which explains the observed vibrational dynamics. The peaks in the ratios of the squared autocorrelation functions are also explained in terms of the evolving geometries of the water cation.
Subfemtosecond quantum dynamics studies of all water isotopomers in the X̃ (2)B1 and à (2)A1 electronic states of the cation formed by Franck-Condon ionization of the neutral ground electronic state are reported. Using the ratio of the autocorrelation functions for the isotopomers as obtained from the solution of the time-dependent Schrödinger equation in a grid representation, high-order harmonic generation signals are calculated as a function of time. The results are found to be in agreement with the available experimental findings and with our earlier study for D2O(+)/H2O(+). Maxima are predicted in the autocorrelation function ratio at various times. Their origin and occurrence is explained by calculating expectation values of the bond lengths and bond angle of the water isotopomers as a function of time. The values so calculated for the (2)B1 and (2)A1 electronic states of the cation show quasiperiodic oscillations that can be associated with the time at which the nuclear wave packet reaches the minima of the potential energy surface, there being responsible for the peaks in the HHG signals.
We have performed numerical nonperturbative simulations of transient absorption pump-probe responses for a series of molecular model systems. The resulting signals as a function of the laser field strength and the pump-probe delay time are compared with those obtained in the perturbative response function formalism. The simulations and their theoretical analysis indicate that the perturbative description remains valid up to moderately strong laser pulses, corresponding to a rather substantial depopulation (population) of the initial (final) electronic states.
We present a description of resonant femtosecond stimulated Raman spectra, which is based on the solution of the nonperturbative equation of motion of the chromophore in the laser fields. The theory is applicable for arbitrary shapes and durations of the Raman pulses, accounts for excited-state absorption, and describes nonstationary preparation of the system by an actinic pulse. The method is illustrated by the calculation of femtosecond stimulated Raman spectra of a model system with a conical intersection.
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