Nonlinear excitation Nonlinearity

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. 

Much of the previous section dealt with two-level systems. Real molecules, however, are not two-level systems for many purposes there are only two electronic states that participate, but each of these electronic states has many states corresponding to different quantum levels for vibration and rotation. A coherent femtosecond pulse has a bandwidth which may span many vibrational levels when the pulse impinges on the molecule it excites a coherent superposition of all tliese vibrational states—a vibrational wavepacket. In this section we deal with excitation by one or two femtosecond optical pulses, as well as continuous wave excitation in section A 1.6.4 we will use the concepts developed here to understand nonlinear molecular electronic spectroscopy. 

The pioneering use of wavepackets for describing absorption, photodissociation and resonance Raman spectra is due to Heller [12, 13,14,15 and 16]- The application to pulsed excitation, coherent control and nonlinear spectroscopy was initiated by Taimor and Rice ([17] and references therein). 

As described at the end of section Al.6.1. in nonlinear spectroscopy a polarization is created in the material which depends in a nonlinear way on the strength of the electric field. As we shall now see, the microscopic description of this nonlinear polarization involves multiple interactions of the material with the electric field. The multiple interactions in principle contain infomiation on both the ground electronic state and excited electronic state dynamics, and for a molecule in the presence of solvent, infomiation on the molecule-solvent interactions. Excellent general introductions to nonlinear spectroscopy may be found in [35, 36 and 37]. Raman spectroscopy, described at the end of the previous section, is also a nonlinear spectroscopy, in the sense that it involves more than one interaction of light with the material, but it is a pathological example since the second interaction is tlirough spontaneous emission and therefore not proportional to a driving field... 

A nice example of this teclmique is the detennination of vibrational predissociation lifetimes of (HF)2 [55]. The HF dimer has a nonlinear hydrogen bonded structure, with nonequivalent FIF subunits. There is one free FIF stretch (v ), and one bound FIF stretch (V2), which rapidly interconvert. The vibrational predissociation lifetime was measured to be 24 ns when excitmg the free FIF stretch, but only 1 ns when exciting the bound FIF stretch. This makes sense, as one would expect the bound FIF vibration to be most strongly coupled to the weak intenuolecular bond. 

From such a treatment, we may derive explicit expressions for the nonlinear radiation in tenns of the linear and nonlinear response and the excitation conditions. For the case of nonlinear reflection, we obtain an irradiance for the radiation emitted at the nonlinear frequency of... 

The higher-order bulk contribution to the nonlmear response arises, as just mentioned, from a spatially nonlocal response in which the induced nonlinear polarization does not depend solely on the value of the fiindamental electric field at the same point. To leading order, we may represent these non-local tenns as bemg proportional to a nonlinear response incorporating a first spatial derivative of the fiindamental electric field. Such tenns conespond in the microscopic theory to the inclusion of electric-quadnipole and magnetic-dipole contributions. The fonn of these bulk contributions may be derived on the basis of synnnetry considerations. As an example of a frequently encountered situation, we indicate here the non-local polarization for SFIG in a cubic material excited by a plane wave (co) ... 

An interferometric method was first used by Porter and Topp [1, 92] to perfonn a time-resolved absorption experiment with a -switched ruby laser in the 1960s. The nonlinear crystal in the autocorrelation apparatus shown in figure B2.T2 is replaced by an absorbing sample, and then tlie transmission of the variably delayed pulse of light is measured as a fiinction of the delay This approach is known today as a pump-probe experiment the first pulse to arrive at the sample transfers (pumps) molecules to an excited energy level and the delayed pulse probes the population (and, possibly, the coherence) so prepared as a fiinction of time. 

These quartic equations are solved in an iterative maimer and, as such, are susceptible to convergence difficulties. In any such iterative process, it is important to start with an approximation reasonably close to the final result. In CC theory, this is often achieved by neglecting all of tlie temis tliat are nonlinear in the t amplitudes (because the ts are assumed to be less than unity in magnitude) and ignoring factors that couple different doubly-excited CSFs (i.e. the sum over i, f, m and n ). This gives t amplitudes that are equal to the... 

In recent years, these methods have been greatly expanded and have reached a degree of reliability where they now offer some of the most accurate tools for studying excited and ionized states. In particular, the use of time-dependent variational principles have allowed the much more rigorous development of equations for energy differences and nonlinear response properties [81]. In addition, the extension of the EOM theory to include coupled-cluster reference fiuictioiis [ ] now allows one to compute excitation and ionization energies using some of the most accurate ab initio tools. 

Peyrard M (ed) 1995 Nonlinear Excitations in Biomolecules Les Ulis Editions de Physique)... 

H. Grubmiiller, N. Ehrenhofer, and P. Tavan. Conformational dynamics of proteins Beyond the nanosecond time scale. In M. Peyard, editor. Proceedings of the Workshop Nonlinear Excitations in BiomoleculesMay 30-June 4, 1994, Houches (Prance), Seiten 231-240. Centre de Physique des Houches (France), Springer-Verlag, 1995. 

Standardizing the Method Equations 10.32 and 10.33 show that the intensity of fluorescent or phosphorescent emission is proportional to the concentration of the photoluminescent species, provided that the absorbance of radiation from the excitation source (A = ebC) is less than approximately 0.01. Quantitative methods are usually standardized using a set of external standards. Calibration curves are linear over as much as four to six orders of magnitude for fluorescence and two to four orders of magnitude for phosphorescence. Calibration curves become nonlinear for high concentrations of the photoluminescent species at which the intensity of emission is given by equation 10.31. Nonlinearity also may be observed at low concentrations due to the presence of fluorescent or phosphorescent contaminants. As discussed earlier, the quantum efficiency for emission is sensitive to temperature and sample matrix, both of which must be controlled if external standards are to be used. In addition, emission intensity depends on the molar absorptivity of the photoluminescent species, which is sensitive to the sample matrix. 

The application of nonlinear optical recording techniques for reversible optical data storage based on the excitation of photochromic molecules by two-photon processes also has been described (154). 

Fig. 1. Representative device configurations exploiting electrooptic second-order nonlinear optical materials are shown. Schematic representations are given for (a) a Mach-Zehnder interferometer, (b) a birefringent modulator, and (c) a directional coupler. In (b) the optical input to the birefringent modulator is polarized at 45 degrees and excites both transverse electric (TE) and transverse magnetic (TM) modes. The appHed voltage modulates the output polarization. Intensity modulation is achieved using polarizing components at the output.

The use of this theory in studies of nonlinear oscillations was suggested in 1929 (by Andronov). At a later date (1937) Krylov and Bogoliubov (K.B.) simplified somewhat the method of attack by a device resembling Lagrange s method of the variation of parameters, and in this form the method became useful for solving practical problems. Most of these early applications were to autonomous systems (mainly the self-excited oscillations), but later the method was extended to... 

It was observed that with a linear circuit and in the absence of any source of energy (except probably the residual charges in condensers) the circuit becomes self-excited and builds up the voltage indefinitely until the insulation is punctured, which is in accordance with (6-138). In the second experiment these physicists inserted a nonlinear resistor in series with the circuit and obtained a stable oscillation with fixed amplitude and phase, as follows from the analysis of the differential equation (6-127). 

L. Mandelstam and N. Papalexi performed an interesting experiment of this kind with an electrical oscillatory circuit. If one of the parameters (C or L) is made to oscillate with frequency 2/, the system becomes self-excited with frequency/ this is due to the fact that there are always small residual charges in the condenser, which are sufficient to produce the cumulative phenomenon of self-excitation. It was found that in the case of a linear oscillatory circuit the voltage builds up beyond any limit until the insulation is ultimately punctured if, however, the system is nonlinear, the amplitude reaches a stable stationary value and oscillation acquires a periodic character. In Section 6.23 these two cases are represented by the differential equations (6-126) and (6-127) and the explanation is given in terms of their integration by the stroboscopic method. 

Nonanalytic Nonlinearities.—A somewhat different kind of nonlinearity has been recognized in recent years, as the result of observations on the behavior of control systems. It was observed long ago that control systems that appear to be reasonably linear, if considered from the point of view of their differential equations, often exhibit self-excited oscillations, a fact that is at variance with the classical theory asserting that in linear systems self-excited oscillations are impossible. Thus, for instance, in the van der Pol equation... 

Ivanov A. A., Kamalov V. F., Koroteev N. I., Orlov R. Yu. Nonlinear and luminescence spectroscopy of vibrationally and electronically excited... 

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