The dynamics of highly excited electronic systems: applications of the electron force field.
Highly excited heterogeneous complex materials are essential elements of important processes, ranging from inertial confinement fusion to semiconductor device fabrication. Understanding the dynamics of these systems has been challenging because of the difficulty in extracting mechanistic information from either experiment or theory. We describe here the electron force field (eFF) approximation to quantum mechanics which provides a practical approach to simulating the dynamics of such systems. eFF includes all the normal electrostatic interactions between electrons and nuclei and the normal quantum mechanical description of kinetic energy for the electrons, but contains two severe approximations: first, the individual electrons are represented as floating Gaussian wave packets whose position and size respond instantaneously to various forces during the dynamics; and second, these wave packets are combined into a many-body wave function as a Hartree product without explicit antisymmetrization. The Pauli principle is accounted for by adding an extra spin-dependent term to the Hamiltonian. These approximations are a logical extension of existing approaches to simulate the dynamics of fermions, which we review. In this paper, we discuss the details of the equations of motion and potentials that form eFF, and evaluate the ability of eFF to describe ground-state systems containing covalent, ionic, multicenter, and/or metallic bonds. We also summarize two eFF calculations previously reported on electronically excited systems: (1) the thermodynamics of hydrogen compressed up to ten times liquid density and heated up to 200,000 K; and (2) the dynamics of Auger fragmentation in a diamond nanoparticle, where hundreds of electron volts of excitation energy are dissipated over tens of femtoseconds. These cases represent the first steps toward using eFF to model highly excited electronic processes in complex materials.
Su
Julius T
JT
Materials and Process Simulation Center, MC 139-74, Caltech, Pasadena, California 91125, USA.
Goddard
William A
WA
D000473:Alkanes / Q000737:chemistry; D002244:Carbon / Q000737:chemistry; D004583:Electrons; D006859:Hydrogen / Q000737:chemistry; D007700:Kinetics; D008670:Metals / Q000737:chemistry; D008968:Molecular Conformation; D056004:Molecular Dynamics Simulation; D011789:Quantum Theory; D055672:Static Electricity; D013696:Temperature; D013816:Thermodynamics
D000473:Alkanes; D008670:Metals; D002244:Carbon; D006859:Hydrogen