- Book Chapter
3
- 10.1007/3-540-35426-3_7
Intermolecular Forces and Generalized Response Functions in Liouville Space
- Jan 01, 2006
- S Mukamel + 2 more +2
Consider two interacting sub-systems with nonoverlapping charge distributions. How can the properties of the combined system be expressed in terms of properties of the individual sub-systems alone? This general problem appears in a wide variety of physical, chemical, and biological systems [Joester 2003, Stone 1996, Moore 2001]. In this chapter we provide a prescription for addressing this issue by the computation of (i) response functions and (ii) correlation functions of spontaneous fluctuations of relevant degrees of freedom in the individual sub-systems. The computation of response and correlation functions is greatly simplified by using the density matrix in Liouville space [Mukamel 1995]. Hilbert and Liouville spaces offer very different languages for the description of nonlinear response. Computing dynamical observables in terms of the wavefunction in Hilbert space requires both forward and backward propagations in time. In contrast, the density matrix calculated in Liouville space should only be propagated forward. The choice is between following only the ket, moving it both forward and backward, or following the joint forward dynamics of the ket and the bra. Artificial time variables (Keldysh loops) commonly used in many-body theory [Haug 1996] are connected with the wavefunction. The density matrix which uses the real laboratory time throughout the calculation offers a more intuitive picture. Wavefunction-based theories calculate transition amplitudes, which by themselves are not observable. The density matrix, on the other hand directly calculates physical observables. Moreover, dephasing processes (damping of off-diagonal elements of the density matrix caused by phase fluctuations) which are naturally included into the Liouville space formulation may not be described in terms of the wavefunction. The “causality paradox” of TDDFT [Gross 1996] can be clearly resolved in Liouville space [Mukamel 2005]. In this chapter we present a method for expressing the joint response of two interacting sub-systems in terms of their correlation and response functions. This factorization appears quite naturally in Liouville space. The p order response of the individual systems is a linear combination of 2 distinct (p + 1)-point correlation functions known as Liouville space pathways [Mukamel 1995], which differ by whether the interaction at each time
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