The experimental observables in coherent, multiple pulse infrared spectroscopic measurements can be calculated from the nonlinear response functions describing the nuclear dynamics of molecular and condensed phase systems. Within classical mechanics, these nonlinear response functions can be expressed in terms of the monodromy matrices that quantify the stability of classical trajectories. We use an ensemble of noninteracting, anharmonic oscillators to examine the effects of the divergence in time of the classical stability matrix on the analytic properties of the third-order response function, relevant to vibrational echo spectroscopy. The twopulse echo measurement is designed to rephase a macroscopic variable, that is, to reverse the effects of destructive interference among the dynamics of microscopic systems characterized by a static distribution of energies. Within classical mechanics, this rephasing is shown to preserve the growth with time of the nonlinear response function that is the signature of the divergence of nearby trajectories. For systems with nearly classical nuclear motions, the vibrational echo measurement may then be interpreted as a probe of the stability of atomic trajectories. I. Introduction Observables in nonlinear infrared and Raman measurements 1-7 of nuclear motions may be computed from nonlinear response functions characterizing the material system. The challenges posed by computing nonlinear response functions for large anharmonic systems with time-dependent quantum mechanics has motivated the analysis of these quantities within classical mechanics. 8-17 Nonlinear response functions of a classical mechanical system may not be calculated directly from a conventional, equilibrium molecular dynamics simulation, because their computation requires knowledge of stability matrices, 8 which quantify the effects of small deviations in initial conditions on classical trajectories. An alternative to simulating nonlinear response functions, which obviates the need to compute stability matrices, is to perform a nonequilibrium molecular dynamics simulation of the material system in the presence of an electromagnetic field and to evaluate numerically the appropriate low-field limit. 15-17 The relevance of stability matrices to nonlinear optical measurements is intuitively clear.
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