Steric effect: A quantitative description from density functional theory

The concepts of steric energy, steric potential, and steric charge are introduced within the density functional theory framework. The steric energy, representing a hypothetical state with all electrons packed into the lowest orbital and other effects entirely excluded, is a measure of the intrinsic space occupied by an electronic system. It is exclusive, repulsive, and extensive, and it vanishes for homogeneous electron gas. When Bader's zero-flux boundary condition is adopted, atoms in molecules are found to achieve balanced steric repulsion among one another with vanished steric energy density interfaces. A few molecular systems involving conformation changes and chemical reactions have been investigated to examine the relative contribution of the steric and other effects, providing insights for a few controversial topics from a different perspective

Observation of sub-Doppler absorption in the /Lambda-type three-level Doppler-broadened cesium system

Thanks to the atomic coherence in coupling laser driven atomic system, sub-Doppler absorption has been observed in Doppler-broadened cesium vapor cell via the /Lambda-type three-level scheme. The linewidth of the sub-Doppler absorption peak become narrower while the frequency detuning of coupling laser increases. The results are in agreement with the theoretical prediction by G. Vemuri et al.[PRA,Vol.53(1996) p.2842].Comment: 12 pages, 5 figures, to appear on Applied Physics

Necessary and sufficient conditions for the N -representability of density functionals

It is well known that variational optimization of the energy using approximate density functionals can give results below the true ground-state energy. This can be attributed to the fact that many approximate density functionals are not N-representable. This paper presents a general method for deriving N-representability conditions in density-functional theory and presents specific results for the kinetic energy, the electron-electron interaction energy, the Hohenberg-Kohn functional, and the exchange-correlation energy functional. The method can be extended to energy densities, and specific results are presented for two different choices of the kinetic-energy density. Max-min variational principles for minimizing the energy subject to N-representability constraints are presented. Some constraints on exchange-correlation density functionals are among our secondary findings. In particular, we construct an exact meta-generalized-gradient-approximation (meta-GGA) functional using a Legendre transform and use this expression to show that (a) meta-GGAs should be convex functionals of the kinetic-energy density and (b) the sum of the Coulomb energy and the meta-GGA exchange-correlation energy should be a convex functional of the electron density