Molecules, Vol. 24, Pages 3660: Superadiabatic Forces via the Acceleration Gradient in Quantum Many-Body Dynamics (Molecules)

We apply the formally exact quantum power functional framework (J. Chem. Phys. 2015, 143, 174108) to a one-dimensional Hooke`s helium model atom. The physical dynamics are described on the one-body level beyond the density-based adiabatic approximation. We show that gradients of both the microscopic velocity and acceleration field are required to correctly describe the effects due to interparticle interactions. We validate the proposed analytical forms of the superadiabatic force and transport contributions by comparison to one-body data from exact numerical solution of the Schrödinger equation. Superadiabatic contributions beyond the adiabatic approximation are important in the dynamics and they include effective dissipation.