Molecule coherence properties

This section begins with a brief description of the basic light-molecule interaction. As already indicated, coherent light pulses excite coherent superpositions of molecular eigenstates, known as wavepackets , and we will give a description of their motion, their coherence properties, and their interplay with the light. Then we will turn to linear and nonlinear spectroscopy, and, finally, to a brief account of coherent control of molecular motion. 

An inherent limitation of mode-selective methods is that Nature does not always provide a local mode that coincides with the channel of interest. One way to circumvent the natural reactive propensities of a molecule is to exploit the coherence properties of the quantum mechanical wave function that describes the motion of the particle. These properties may be imparted to a reacting molecule by building them first into a light source and then transferring them to the molecular wave function by means of a suitable excitation process. 

Figure 45. Schematic representation of the preparation and detection of rotational coherence in a molecule. The case depicted corresponds to the linearly polarized excitation (polarization vector ,) of a symmetric top molecule in ground-state ro-vibronic level S0v0 J0K0M0) to those rotational levels of the excited vibronic state 15,1 ,) allowed by the rotational selection rules germane to a parallel-type transition moment. The excitation process creates a superposition state of three rotational levels, the coherence properties of which can be probed by time resolving the polarized fluorescence (polarization it) to the manifold of ground-state ro-vibronic levels S0vf JfKfMfy, or by probing with a second, variably time-delayed laser pulse (polarization...

Time-domain spectroscopies entail a major shift in emphasis from traditional spectroscopies, since the experimenter can control, in principle, the duration, shape, and sequence of pulses. One may say that traditional, CW spectroscopy, is passive—the experimenter attempts to study static properties of a particular molecule. Coherent pulse experiments are active in that, given a set of molecular properties (which may in fact be known from various spectroscopies), one tries to arrange for a desired chemical product, or to design a pulse sequence that will probe new molecular properties. The time-dependent quantum mechanics-wavepacket dynamics approach developed here is a natural framework for formulating and interpreting new multiple pulse experiments. Femtosecond experiments yield to a particularly simple interpretation within our approach. 

We now examine, as a first case of exploitation of the coherence properties of the coupled molecule-electromagnetic field system, a representation of CARS... 

In the interaction of a coherent laser beam with an ensemble of particles (atoms or molecules), one may treat the individual particles as nearly stationary, because even for a fast atomic/molecular beam the particles move only a few micrometres on the time-scale of the photon interaction. Consequently, if the laser photons are absorbed in the interaction, the coherence properties of the laser radiation are transferred to the particle ensemble. It is this coherence transfer that is exploited in experiments such as the orientation of reagents in chemical reactions, or the probing of intramolecular motion in transition states and orientation of products. 

Many experiments employing LIF to extract the population and or the anisotropy of the nascent angular momentum distribution are carried out with pulsed lasers exhibiting rather limited coherence properties. Under these conditions coherence between the lower and excited state may be neglected and the more simple rate equational approach to model the laser-molecule interaction is appropriate. 

Let us emphasize that noncoherent laser control of molecules depends on differences in the absorption spectrum between different molecular species, for example isotopic molecules. Coherent laser control is distinguished by its nontrivial manipulation of the phase coherence of excited states in molecules that can be similar in their absorption spectra but different in their phase coherence properties (Brixner et al. 20016). 

Two types of observations show that our model of a gas must be refined. The qualitative observation is that gases can be condensed to liquids when cooled or compressed. This property strongly suggests that, contrary to the assumptions of the kinetic model, gas molecules do attract one another because otherwise they would not cohere (stick together). In addition, liquids are very difficult to compress. This... 

From a theoretical perspective, the object that is initially created in the excited state is a coherent superposition of all the wavefunctions encompassed by the broad frequency spread of the laser. Because the laser pulse is so short in comparison with the characteristic nuclear dynamical time scales of the motion, each excited wavefunction is prepared with a definite phase relation with respect to all the others in the superposition. It is this initial coherence and its rate of dissipation which determine all spectroscopic and collisional properties of the molecule as it evolves over a femtosecond time scale. For IBr, the nascent superposition state, or wavepacket, spreads and executes either periodic vibrational motion as it oscillates between the inner and outer turning points of the bound potential, or dissociates to form separated atoms, as indicated by the trajectories shown in Figure 1.3. 

Taken together, our MD simulahons of acetylcholine and carnosine emphasize the marked difference between them. Indeed, acetylcholine is representative of a sensitive molecule whose physicochemical and structural properties can vary in a coherent manner, aptly adapting themselves to the simulated media. Conversely,... 

From the point of view of the study of dynamics, the laser has three enormously important characteristics. Firstly, because of its potentially great time resolution, it can act as both the effector and the detector for dynamical processes on timescales as short as 10 - s. Secondly, due to its spectral resolution and brightness, the laser can be used to prepare large amounts of a selected quantum state of a molecule so that the chemical reactivity or other dynamical properties of that state may be studied. Finally, because of its coherence as a light source the laser may be used to create in an ensemble of molecules a coherent superposition of states wherein the phase relationships of the molecular and electronic motions are specified. The dynamics of the dephasing of the molecular ensemble may subsequently be determined. 

In contrast to spontaneous emission, induced emission (also called stimulated emission) is coherent, i.e. all emitted photons have the same physical characteristics - they have the same direction, the same phase and the same polarization. These properties are characteristic of laser emission (L.A.S.E.R. = Light Amplification by Stimulated Emission of Radiation). The term induced emission comes from the fact that de-excitation is triggered by the interaction of an incident photon with an excited atom or molecule, which induces emission of photons having the same characteristics as those of the incident photon. 

Technically important electrochemical reactions of pyrrole and thiophene involve oxidation in non-nucleophilic solvents when the radical-cation intermediates react with the neutral molecule causing polymer growth [169, 191], Under controlled conditions polymer films can be grown on the anode surface from acetonitrile. Tliese films exhibit redox properties and in the oxidised, or cation doped state, are electrically conducting. They can form the positive pole of a rechargeable battery system. Pyrroles with N-substituents are also polymerizable to form coherent films [192], Films have been constructed to support electroactive transition metal centres adjacent to the electrode surface fomiing a modified electrode,... 

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