Real-Time Time-Dependent Density Functional Theory for Pump-Probe Spectroscopies

Abstract

The last decade has witnessed a rapid advancement in laser technology, enabling the direct monitoring and control of electronic motion on its natural attosecond to sub-femtosecond timescales. Ultrafast processes are conventionally studied using pump-probe spectroscopic techniques, where a pump pulse drives the molecule out of equilibrium and a time-delayed probe pulse records the response of the coherent non-stationary state. Since, these processes are non-linear and non-perturbative in nature, real-time formalisms provide a suitable theoretical framework for studying ultrafast light-induced dynamics. In addition, relativistic effects can play an important role in such simulations, either because the external field lies in the XUV to soft-X-ray region targeting core-level excitations, or because the molecular system contains heavy elements. In this chapter, we provide an overview of recent developments in real-time time-dependent density functional theory for simulating pump-probe spectroscopies (namely, transient absorption and transient electronic circular dichroism) at both non-relativistic and relativistic Hamiltonian levels. In order to further interpret these spectroscopic signals, we analyze several spectroscopically relevant time-dependent sub-observables, such as induced electronic densities and induced dipole moments as well as analytical formulations of generalized non-equilibrium response functions. We provide examples to show that the framework can be used to investigate and design new light-induced phenomena that emerge only in the attosecond regime.