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Abstract

This thesis is focused on classical and semiclassical approximations of a specific quantum time correlation function, the “quantum fidelity.” Namely, we rigorously study the efficiency of a continuous class of algorithms for the evaluation of its classical limit and both the cost and the error of a particular semiclassical approximation of it. In the physics domain, quantum fidelity can be used to study the cross section of inelastic neutron scattering and phenomena like decoherence and irreversibility in NMR experiments. In chemical physics, quantum fidelity can be employed to compute the spectrum of a quantum state, to evaluate the accuracy of quantum dynamics on an approximate potential energy surface, and to verify the importance of nonadiabatic electronic transitions in molecules. Unfortunately, as for any numerical simulation of a quantum dynamical object, many-dimensional calculations of quantum fidelity are extremely expensive computationally. Classical methods, not including any quantum effect, are generally believed to be efficient approximations for the numerical evaluation of large systems’ properties when quantum effects are not important. We prove that, previous to this research, the computational costs of available algorithms for the simulation of classical fidelity increased exponentially with the number of degrees of freedom and we single out, within a continuous family of algorithms, the only one for which the number of trajectories needed for convergence is independent of the system’s dimensionality. Recently a semiclassical method, called “dephasing representation” (DR), has been proposed to approximate quantum fidelity accurately and efficiently. Although semiclassical methods, approximately including all types of quantum effects, are generally more accurate but much less efficient than classical methods, we prove that for the semiclassical DR there exists at least one algorithm for which the number of trajectories needed for convergence is independent of dimensionality and also that this semiclassical algorithm is even faster than the most efficient classical fidelity algorithm previously singled out. Encouraged by the surprising efficiency of the specific semiclassical method, we investigate the error of the DR compared to the quantum benchmark.

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