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Each Unidimensional System is Hamiltonian, so that Each Unidimensional System is Quantizable

Domenico Oricchio

Published Feb 1, 2016• 0 citations
OpenAlex

Abstract

A simple method to obtain the Hamiltonian from each unidimensional dynamical system. Each unidimensional system is so quantizable. It is probable that each multidimensional system is quantizable, because of the generalization of the idea.

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The fast dynamics of molecular polaritonics is scrutinized theoretically through the implementation of two-dimensional spectroscopy protocols. We derive conceptually simple and computationally efficient formulas to calculate two-dimensional spectra for molecules, each of them modeled as a system of two electronic states including vibrational relaxation, immersed in an optical cavity, thus coupled to quantized radiation. Cavity photon losses and molecular relaxation are incorporated into the Hamiltonian dynamics to form an open quantum system that is solved through a master equation. In the collective case, the relaxation dynamics into dark states is revealed to be the crucial factor to explain the asymmetries in both the diagonal and cross peaks of two-dimensional spectra for long waiting times between excitation and detection, a feature shown by recent experiments. Our theoretical method provides a deeper insight in those processes that yield relevant signals in multidimensional molecular spectroscopy.