Ultrafast dynamics with the exact factorization

The exact factorization of the time-dependent electron–nuclear wavefunction has been employed successfully in the field of quantum molecular dynamics simulations for interpreting and simulating light-induced ultrafast processes. In this work, we summarize the major developments leading to the formulation of a trajectory-based approach, derived from the exact factorization equations, capable of dealing with nonadiabatic electronic processes, and including spin-orbit coupling and the non-perturbative effect of an external time-dependent field. This trajectory-based quantum-classical approach has been dubbed coupled-trajectory mixed quantum-classical (CT-MQC) algorithm, whose performance is tested here to study the photo-dissociation dynamics of IBr. Graphic abstract

Asymptotic Behavior of the Exchange-Correlation Energy Density and the Kohn-Sham Potential in Density Functional Theory: Exact Results and Strategy for Approximations

The present work is a review of two analytical properties of the exact exchange-correlation (xc) functional in density-functional theory. These properties are the asymptotic behavior of the xc energy density per particle and the asymptotic behavior of the Kohn-Sham potential, in finite many-electron systems. The derivation of the asymptotic forms for both quantities is reviewed, employing the concepts of the adiabatic connection and of the xc hole with relation to the first quantity and the electron exact factorization approach for the second one. Furthermore, it is shown that the correct asymptotic behavior of one of the aforementioned quantities does not guarantee a correct behavior of the other. In this process, a new quantity, the xc hole response function, is defined and its exact exchange part is analytically derived. The extent to which existing xc approximations satisfy the named exact properties is reviewed and the relationship between correct asymptotics and freedom from one-electron self-interaction in DFT is discussed. Finally, a strategy for development of advanced approximations for exchange and correlation with a correct asymptotic behavior is suggested.<br>

Asymptotic Behavior of the Exchange-Correlation Energy Density and the Kohn-Sham Potential in Density Functional Theory: Exact Results and Strategy for Approximations

The present work is a review of two analytical properties of the exact exchange-correlation (xc) functional in density-functional theory. These properties are the asymptotic behavior of the xc energy density per particle and the asymptotic behavior of the Kohn-Sham potential, in finite many-electron systems. The derivation of the asymptotic forms for both quantities is reviewed, employing the concepts of the adiabatic connection and of the xc hole with relation to the first quantity and the electron exact factorization approach for the second one. Furthermore, it is shown that the correct asymptotic behavior of one of the aforementioned quantities does not guarantee a correct behavior of the other. In this process, a new quantity, the xc hole response function, is defined and its exact exchange part is analytically derived. The extent to which existing xc approximations satisfy the named exact properties is reviewed and the relationship between correct asymptotics and freedom from one-electron self-interaction in DFT is discussed. Finally, a strategy for development of advanced approximations for exchange and correlation with a correct asymptotic behavior is suggested.<br>