On the correspondence between fermion and boson states and operators

Mapping of shell-model (fermion) Hamiltonians onto boson Hamiltonians which underly the interaction boson model ^1–5) is investigated. A simple correspondence is defined and a sufficient condition given for shell-model Hamiltonians to simply correspond to finite hermitian boson Hamiltonians. A special case is discussed where diagonalization of a shell-model Hamiltonian for valence protons and neutrons can be exactly carried out in an equivalent (but different) boson space. If, however, the proton Hamiltonian and neutron Hamiltonian are diagonal in the seniority scheme, mapping of fermion states onto orthogonal boson states cannot be a simple correspondence. In that case the boson quadrupole operators equivalent to fermion guadrupole operators cannot be single-boson operators but must be more complicated, ones.     

Implementability of correlated and communication equilibrium outcomes in incomplete information games

In a correlated equilibrium, the players’ choice of actions is directed by correlated random messages received from an outside source, or mechanism. These messages allow for more equilibrium outcomes than without any messages (pure-strategy equilibrium) or with statistically independent ones (mixed-strategy equilibrium). In an incomplete information game, the messages may also reflect the types of the players, either because they are affected by extraneous factors that also affect the types (correlated equilibrium) or because the players themselves report their types to the mechanism (communication equilibrium). Mechanisms may be further differentiated by the connections between the messages that the players receive and their own and the other players’ types, by whether the messages are statistically dependent or independent, and by whether they are random or deterministic. Consequently, whereas for complete information games there are only three classes of equilibrium outcomes, with incomplete information the corresponding number is 14 or 15 for correlated equilibria and even larger—15, 16 or 17—for communication equilibria. For both solution concepts, the implication relations between the different kinds of equilibria form a two-dimensional lattice, which is considerably more intricate than the single-dimensional one of the complete information case.     

Charge-Shift Bonding: A New and Unique Form of Bonding

Charge-shift bonds (CSBs) constitute a new class of bonds different than covalent/polar-covalent and ionic bonds. Bonding in CSBs does not arise from either the covalent or the ionic structures of the bond, but rather from the resonance interaction between the structures. This Essay describes the reasons why the CSB family was overlooked by valence-bond pioneers and then demonstrates that the unique status of CSBs is not theory-dependent. Thus, valence bond (VB), molecular orbital (MO), and energy decomposition analysis (EDA), as well as a variety of electron density theories all show the distinction of CSBs vis-à-vis covalent and ionic bonds. Furthermore, the covalent–ionic resonance energy can be quantified from experiment, and hence has the same essential status as resonance energies of organic molecules, e.g., benzene. The Essay ends by arguing that CSBs are a distinct family of bonding, with a potential to bring about a Renaissance in the mental map of the chemical bond, and to contribute to productive chemical diversity.     

An efficient algorithm for complete active space valence bond self‐consistent field calculation

This article describes a novel algorithm for the optimization of valence bond self‐consistent field (VBSCF) wave function for a complete active space (CAS), so‐called VBSCF(CAS). This was achieved by applying the strategies adopted in the optimization of CASSCF wave functions to VBSCF(CAS) wave functions, using an auxiliary orthogonal orbital set that generates the same configuration space as the original nonorthogonal orbital set. Theoretical analyses and test calculations show that the VBSCF(CAS) method shares the same computational scaling as CASSCF. The test calculations show the current capability of VBSCF method, which involves millions of VB structures. © 2012 Wiley Periodicals, Inc.     

How and why nanoparticle's curvature regulates the apparent pKa of the coating ligands

Dissociation of ionizable ligands immobilized on nanopaticles (NPs) depends on and can be regulated by the curvature of these particles as well as the size and the concentration of counterions. The apparent acid dissociation constant (pK(a)) of the NP-immobilized ligands lies between that of free ligands and ligands self-assembled on a flat surface. This phenomenon is explicitly rationalized by a theoretical model that accounts fully for the molecular details (size, shape, conformation, and charge distribution) of both the NPs and the counterions.     

Charge‐Shift Bonding: A New and Unique Form of Bonding

Charge‐shift bonds (CSBs) constitute a new class of bonds different than covalent/polar‐covalent and ionic bonds. Bonding in CSBs does not arise from either the covalent or the ionic structures of the bond, but rather from the resonance interaction between the structures. This Essay describes the reasons why the CSB family was overlooked by valence‐bond pioneers and then demonstrates that the unique status of CSBs is not theory‐dependent. Thus, valence bond (VB), molecular orbital (MO), and energy decomposition analysis (EDA), as well as a variety of electron density theories all show the distinction of CSBs vis‐à‐vis covalent and ionic bonds. Furthermore, the covalent–ionic resonance energy can be quantified from experiment, and hence has the same essential status as resonance energies of organic molecules, e.g., benzene. The Essay ends by arguing that CSBs are a distinct family of bonding, with a potential to bring about a Renaissance in the mental map of the chemical bond, and to contribute to productive chemical diversity.