Optical absorption, phase-coherent

The interaction between light and matter can be viewed as the creation of a coherent quantum superposition of initial and final electron states that has an associated polarization [3], as shown in Figure 1. The coherence between states with different wave vector requires an intermediate virtual state and the presence of a coherent phonon. A transition between the initial and final states may occur when the coherence of the system is broken either due to the finite width of an optical wave packet or by scattering from the environment. The transition results in the absorption of a photon and the creation of a hot electron-hole pair. Otherwise, the photon is re-radiated with a different phase and, perhaps, polarisation. 

Coherent light sources are characterized by a spectral intensity distribution E(oj) and a frequency-dependent phase 0(w). According to first-order perturbation theory, linear absorption probabilities are given by the overlap between the spectrum of the light source E(w) and the optical transition, and are independent of the phase function In non-linear processes (2nd... 

Thus far, we have examined vibrational spectroscopy using IR absorption spectroscopy, what we called in Ch. 3 one photon method , a general type that encompasses most experiments in spectroscopy. There exist, however, other types of spectroscopy to observe vibrations. These are for instance Raman spectroscopy, which is also of a current use in chemical physics and may be considered a routine method. Other less known methods are modem time-resolved IR spectroscopies. All these methods are two-photon or multiphoton spectroscopies. They do not involve a single photon, as in absorption, but the simultaneous absorption and emission of two photons, as in Raman and in other scattering experiments, or the successive absorption(s) and emission(s) of photons that are coherently delayed in time, as in time-resolved nonlinear spectroscopies. By coherently , we assume the optical waves that carry these two photons keep a well-defined phase difference. In this latter type of spectroscopy, we include all modem set-ups that involve time-controlled laser spectroscopic techniques. We briefly sketch the interest of these various methods for the study of H-bonds in the following subsections. 

Phase-dependent coherence and interference can be induced in a multi-level atomic system coupled by multiple laser fields. Two simple examples are presented here, a three-level A-type system coupled by four laser fields and a four-level double A-type system coupled also by four laser fields. The four laser fields induce the coherent nonlinear optical processes and open multiple transitions channels. The quantum interference among the multiple channels depends on the relative phase difference of the laser fields. Simple experiments show that constructive or destructive interference associated with multiple two-photon Raman channels in the two coherently coupled systems can be controlled by the relative phase of the laser fields. Rich spectral features exhibiting multiple transparency windows and absorption peaks are observed. The multicolor EIT-type system may be useful for a variety of application in coherent nonlinear optics and quantum optics such as manipulation of group velocities of multicolor, multiple light pulses, for optical switching at ultra-low light intensities, for precision spectroscopic measurements, and for phase control of the quantum state manipulation and quantum memory. 

In all these time-resolved experiments the principles of pump-probe laser spectroscopy are the key element in the experimental design. A laser pulse is optically split into two components of unequal amplitude. The intense fraction, acting as a pump piilse, is directed towards the target or sample cell to trigger the molecular event under study. The much attenuated probe pulse monitors the absorption, raman scattering, polarization, coherence, or phase shift, which is linked explicitly to the dynamical observable under investigation. Extremely precise time... 

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