In local effective potential energy theories such as the Hohenberg-Kohn-Sham density functional theory (HKS-DFT) and quantal density functional theory (Q-DFT), electronic systems in their ground or excited states are mapped to model systems of noninteracting fermions with equivalent density. From these models, the equivalent total energy and ionization potential are also obtained. This paper co...

The derivation of the nucleon-nucleon force from the Skyrme model is reexamined. Starting from previous results for the potential energy of quasistatic solutions, we show that a calculation using the Born-Oppenheimer approximation properly taking into account the mixing of nucleon resonances, leads to substantial central attraction. We obtain a potential that is in qualitative agreement with ph...

The equilibrium structure and potential energy surface of beryllium dihydride BeH(2) in its ground electronic state have been determined from highly accurate ab initio calculations. The vibration-rotation energy levels of three isotopomers BeH(2), BeD(2), and BeHD were predicted using the variational method. The calculated spectroscopic constants are in remarkably good agreement with the existi...

In this paper, we continue our studies of the phase space geometry and dynamics associated with index k saddles (k > 1) of the potential energy surface. Using Poincaré-Birkhoff normal form (NF) theory, we give an explicit formula for a "dividing surface" in phase space, i.e., a codimension one surface (within the energy shell) through which all trajectories that "cross" the region of the index ...

The Huggins band of ozone is investigated by means of exact dynamics calculations using a new (diabatic) potential energy surface for the (1)B(2) state. The remarkable agreement with the measured spectrum strongly suggests that the Huggins band is due to the two C(s) potential wells of the (1)B(2) state. The vibrational assignment, based on the nodal structure of wave functions, supports the mo...

The potential energy surfaces for the reaction between H2O and the protonated alcohols MeOH2+, EtOH2+, PriOH2+, and Bu(t)OH2+ have been explored by means of high level ab initio theoretical methods. Both nucleophilic substitution (SN2) and elimination (E2) pathways have been investigated. Front side (SNF) and the familiar back side (SNB) Walden inversion attack of the nucleophile have been foun...

By mapping out potential energy surfaces from density-functional theory (DFT) and solving a protonic Schrödinger equation, we find that the H atom in a unit cell of the Li2NH crystal shows remarkably strong quantum behavior, leading to the delocalization of H over six octahedral sites around each N. This can be rationalized in terms of rapid coherent tunneling among these equivalent octahedral ...

We use computer simulations to study the thermodynamic properties of a glass-former in which a fraction c of the particles has been permanently frozen. By thermodynamic integration, we determine the Kauzmann, or ideal glass transition, temperature [Formula: see text] at which the configurational entropy vanishes. This is done without resorting to any kind of extrapolation, i.e., [Formula: see t...

Density-corrected DFT is a method that cures several failures of self-consistent semilocal DFT calculations by using a more accurate density instead. A novel procedure employs the Hartree-Fock density to bonds that are more severely stretched than ever before. This substantially increases the range of accurate potential energy surfaces obtainable from semilocal DFT for many heteronuclear molecu...

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