The nonlinear optical response of a system of molecules often contains contributions whereby the products of lower-order processes in two separate molecules give signals that appear on top of a genuine direct higher-order process with a single molecule. These many-body contributions are known as cascading and complicate the interpretation of multidimensional stimulated Raman and other nonlinear signals. In a quantum electrodynamic treatment, these cascading processes arise from second-order expansion in the molecular coupling to vacuum modes of the radiation field, i.e., single-photon exchange between molecules, which also gives rise to other collective effects. We predict the relative phase of the direct and cascading nonlinear signals and its dependence on the microscopic dynamics as well as the sample geometry. This phase may be used to identify experimental conditions for distinguishing the direct and cascading signals by their phase. Higher-order cascading processes involving the exchange of several photons between more than two molecules are discussed.
The nonlinear optical response of a system of molecules often contains contributions whereby the products of lower-order processes in two separate molecules give signals that appear on top of a genuine direct higher-order process with a single molecule. These many-body contributions are known as cascading and complicate the interpretation of multidimensional stimulated Raman and other nonlinear signals. In a quantum electrodynamic treatment, these cascading processes arise from second-order expansion in the molecular coupling to vacuum modes of the radiation field, i.e., single-photon exchange between molecules, which also gives rise to other collective effects. We predict the relative phase of the direct and cascading nonlinear signals and its dependence on the microscopic dynamics as well as the sample geometry. This phase may be used to identify experimental conditions for distinguishing the direct and cascading signals by their phase. Higher-order cascading processes involving the exchange of several photons between more than two molecules are discussed.
The semi-classical theory of radiation-matter coupling misses local-field effects that may alter the pulse time-ordering and cascading that leads to the generation of new signals. These are then introduced macroscopically by solving Maxwell's equations. This procedure is convenient and intuitive but ad hoc. We show that both effects emerge naturally by including coupling to quantum modes of the radiation field that are initially in the vacuum state to second order. This approach is systematic and suggests a more general class of corrections that only arise in a QED framework. In the semi-classical theory, which only includes classical field modes, the susceptibility of a collection of N non-interacting molecules is additive and scales as N. Second-order coupling to a vacuum mode generates an effective retarded interaction that leads to cascading and local field effects both of which scale as N(2).
Nonlinear optical signals from an assembly of N noninteracting particles consist of an incoherent and a coherent component, whose magnitudes scale ~ N and ~ N(N - 1), respectively. A unified microscopic description of both types of signals is developed using a quantum electrodynamical (QED) treatment of the optical fields. Closed nonequilibrium Green's function expressions are derived that incorporate both stimulated and spontaneous processes. General (n + 1)-wave mixing experiments are discussed as an example of spontaneously generated signals. When performed on a single particle, such signals cannot be expressed in terms of the nth order polarization, as predicted by the semiclassical theory. Stimulated processes are shown to be purely incoherent in nature. Within the QED framework, heterodyne-detected wave mixing signals are simply viewed as incoherent stimulated emission, whereas homodyne signals are generated by coherent spontaneous emission.
By applying a sufficiently intense beam of off-resonant light, simultaneously with a conventional excitation source beam, the efficiencies of one- and two-photon absorption processes may be significantly modified. The nonlinear mechanism that is responsible, known as laser modified absorption, is fully described by a quantum electrodynamical analysis. The origin of the process, which involves stimulated forward Rayleigh-scattering of the auxiliary beam, relates to higher order terms which are secured by a time-dependent perturbation treatment. These terms, usually inconsequential when a single beam of light is present, become prominent under the secondary optical stimulus – even with levels of intensity that are moderate by today’s standards. Distinctive kinds of behaviour may be observed for chromophores fixed in a static arrangement, or for solution- or gas-phase molecules whose response is tempered by a rotational average of orientations. In each case the results exhibit an interplay of factors involving the beam polarisations and the molecular electronic response. Special attention is given to interesting metastable states that are symmetry forbidden by one- or two-photon absorption. Such states may be accessible, and thus become populated, on input of the auxiliary beam. For example, in the one-photon absorption case, terms arise that are more usually associated with three-photon processes, corresponding to very different selection rules. Other kinds of metastable state also arise in the two-photon process, and measuring the effect of applying the stimulus beam to absorbances of such character adds a new dimension to the information content of the associated spectroscopy. Finally, based on these novel forms of optical nonlinearity, there may be new possibilities for quantum non-demolition measurements.
Spectroscopy, the study of matter via its interactions with light, is a vast subject that includes many of humanity's principle means of probing the fundamental structure of matter. Though usually understood from the perspective of classical light, important effects arise due to the quantum nature of the electromagnetic field. Additionally, the quantum vacuum can serve as an effective couple between molecules in the system, generating many-body interactions and cooperative processes in the material. While many techniques are well-described classically, quantum-field corrections can dominate the desired signals in certain cases, such as cascading in higher-order n-wave mixing signals, and are key for experimental interpretation. Even spontaneous emission and light scattering are best understood from the perspective of quantum fields. In this thesis, we utilize a systematic procedure, based on the density matrix in Liouville space, to give a rigorous description of elementary quantum-field effects in nonlinear spectroscopy, with specific examples made to ultrafast x-ray and optical techniques.
Abstract In broadband quantum optical systems, nonlinear interactions among a large number of frequency components induce complex dynamics that may defy heuristic analysis. In this work we introduce a perturbative framework for factoring out reservoir degrees of freedom and establishing a concise effective model (effective field theory) for the remaining system. Our approach combines approximate diagonalization of judiciously partitioned subsystems with master equation techniques. We consider cascaded optical χ ( 2 ) (quadratic) nonlinearities as an example and show that the dynamics can be construed (to leading order) as self-phase modulations of dressed fundamental modes plus cross-phase modulations of dressed fundamental and second-harmonic modes. We then formally eliminate the second-harmonic degrees of freedom and identify emergent features of the fundamental wave dynamics, such as two-photon loss channels, and examine conditions for accuracy of the reduced model in dispersive and dissipative parameter regimes. Our results highlight the utility of system-reservoir methods for deriving accurate, intuitive reduced models for complex dynamics in broadband nonlinear quantum photonics, and may help guide quantum technological proposals in emerging systems where quantum effects become significant at the single-photon level.