High-frequency limit of spectroscopy

We consider an arbitrary quantum mechanical system, initially in its ground-state, exposed to a timedependent electromagnetic pulse with a carrier frequency omega(0) and a slowly varying envelope of finite duration. By working out a solution to the time-dependent Schrodinger equation in the high-!0 limit, we find that, to the leading order in omega(0), a perfect self-cancellation of the system's linear response occurs as the pulse switches off. Surprisingly, the system's observables are, nonetheless, describable in terms of a combination of its linear density response function and nonlinear functions of the electric field. An analysis of jellium slab and jellium sphere models reveals a very high surface sensitivity of the considered setup, producing a richer excitation spectrum than accessible within the conventional linear response regime. On this basis, we propose a new spectroscopic technique, which we provisionally name the Nonlinear High-Frequency Pulsed Spectroscopy (NLHFPS). Combining the advantages of the extraordinary surface sensitivity, the absence of constraints by the traditional dipole selection rules, and the clarity of theoretical interpretation utilizing the linear response time-dependent density functional theory, NLHFPS has a potential to evolve into a powerful characterization method for nanoscience and nanotechnology.

Automated summary

This article investigates the response of an arbitrary quantum mechanical system to a finite duration pulsed electromagnetic radiation. It is found that the system's linear response cancels out completely when the pulse switches off, but the observables can still be described using a combination of linear density response function and nonlinear functions of the electric field. Analysis of jellium slab and jellium sphere models reveals a high surface sensitivity, resulting in a richer excitation spectrum compared to the conventional linear response regime. Based on this, a new spectroscopic technique called Nonlinear High-Frequency Pulsed Spectroscopy (NLHFPS) is proposed.