Density functional theory of freezing of a system of highly elongated ellipsoidal oligomer solutions

We have used the density functional theory of freezing to study the liquid crystalline phase behavior of a system of highly elongated ellipsoidal conjugated oligomers dispersed in three different solvents namely chloroform, toluene and their equimolar mixture. The molecules are assumed to interact via solvent-implicit coarse-grained Gay–Berne potential. Pair correlation functions needed as input in the density functional theory have been calculated using the Percus–Yevick (PY) integral equation theory. Considering the isotropic and nematic phases, we have calculated the isotropic–nematic phase transition parameters and presented the temperature–density and pressure–temperature phase diagrams. Different solvent conditions are found not only to affect the transition parameters but also determine the capability of oligomers to form nematic phase in various thermodynamic conditions. In principle, our results are verifiable through computer simulations.     

Density wave theory of freezing and the solid

The theory of the liquid to solid transition, in three as well as in two dimensions, is reviewed. The transition can be viewed either as the melting of the solid due to phonon or defect proliferation instabilities or alternatively as freezing of the liquid into a density wave state with crystalline symmetry. A theory due to Yussouff and the author, based on the latter idea, is discussed and its predictions are compared with experiment. It is shown that the theory leads to a new approach to the properties of a deformed (e.g., sheared) solid and of defects such as grain boundaries and dislocations in a solid. The approach brings out explicitly the structural nature of these properties, and is not restricted to small deviations from perfect periodicity (harmonic approximation) since the solid, the liquid and anything in between can be handled theoretically.     

Density functional theory in transition-metal chemistry: a self-consistent Hubbard U approach

Transition-metal centers are the active sites for a broad variety of biological and inorganic chemical reactions. Notwithstanding this central importance, density-functional theory calculations based on generalized-gradient approximations often fail to describe energetics, multiplet structures, reaction barriers, and geometries around the active sites. We suggest here an alternative approach, derived from the Hubbard U correction to solid-state problems, that provides an excellent agreement with correlated-electron quantum chemistry calculations in test cases that range from the ground state of Fe2 and Fe2- to the addition elimination of molecular hydrogen on FeO+. The Hubbard U is determined with a novel self-consistent procedure based on a linear-response approach.     

Density functional approach to quantum lattice systems

For quantum lattice systems, we consider the problem of characterizing the set of single-particle densities,, which come from the ground-state eigenspace of someN-particle Hamiltonian of the form whereH ₀ is a fixed, bounded operator representing the kinetic and interaction energies. We show that the conditions on are that it be strictly positive, properly normalized, and consistent with the Pauli principle. Our results are valid for both finite and infinite lattices and for either bosons or fermions. The Coulomb interaction may be included inH ₀ if the lattice dimension is 2. We also characterize those single-particle densities which come from the Gibbs states of such Hamiltonians at finite temperature. In addition to the conditions stated above, must satisfy a finite entropy condition.Research supported by the National Science Foundation under grant No. PHY-82-03669.Research supported by Office of Naval Research under grant No. 0014-80-G-0084.On leave from Department of Mathematics, University of Lowell, Massachusetts 01854.     

Density functional theory of fermion condensation

A density functional formulation of the fermion condensation is presented. It is demonstrated that the standard Kohn-Sham scheme is not valid beyond the fermion condensation phase transition since the functional starts to depend on the quasiparticle density matrix. Our consideration also furnishes an opportunity to calculate the real single particle excitation spectra of superconducting systems within the density functional theory.     

Density functional theory of heterogeneous crystallization

This mini-review summarizes recent progress in describing heterogeneous crystallization processes and microstructure formation within microscopic classical density functional theory (DFT). After outlining the basic features of DFT, we discuss several applications ranging from the structure and thermodynamics of fluid-crystal interfaces for hard sphere and Yukawa systems to dynamical phenomena such as crystal growth on structured substrates and induced by externally imposed seeds.     

Density functional theory: Foundations reviewed

Guided by the above motto (quotation), we review a broad range of issues lying at the foundations of Density Functional Theory, DFT, a theory which is currently omnipresent in our everyday computational study of atoms and molecules, solids and nano-materials, and which lies at the heart of modern many-body computational technologies. The key goal is to demonstrate that there are definitely the ways to improve DFT. We start by considering DFT in the larger context provided by reduced density matrix theory (RDMT) and natural orbital functional theory (NOFT), and examine the implications that N$N$-representability conditions on the second-order reduced density matrix (2-RDM) have not only on RDMT and NOFT but, also, by extension, on the functionals of DFT. This examination is timely in view of the fact that necessary and sufficient N$N$-representability conditions on the 2-RDM have recently been attained.     

On aC*-algebra approach to phase transition in the two-dimensional Ising model

We investigate the state on theC*-algebra of Pauli spins on a one-dimensional lattice (infinitely extended in both directions) which gives rise to the thermodynamic limit of the Gibbs ensemble in the two-dimensional Ising model (with nearest neighbour interaction). It is shown that the representation of the Pauli spin algebra associated with the state is factorial above and at the known critical temperature, while it has a two-dimensional center below the critical temperature. As a technical tool, we derive a general criterion for a state of the Pauli spin algebra corresponding to a Fock state of the Fermion algebra to be primary. We also show that restrictions of two quasifree states of the Fermion algebra to its even part are equivalent if and only if the projection operatorsE ₁ andE ₂ (on the direct sum of two copies of the basic Hilbert space) satisfy the following two conditions: (1)E ₁ ?E ₂ is in the Hilbert-Schmidt class, (2)E ₁ ∧ (1 ?E ₂) has an even dimension, where the even-oddness of dimE ₁ ∧ (1 ?E ₂) is called ?₂-index ofE ₁ andE ₂ and is continuous inE ₁ andE ₂ relative to the norm topology.     

Effective field theory and integrability in two-dimensional Mott transition

We study the Mott transition in a two-dimensional lattice spinless fermion model with nearest neighbors density–density interactions. By means of a two-dimensional Jordan–Wigner transformation, the model is mapped onto the lattice XXZ spin model, which is shown to possess a quantum group symmetry as a consequence of a recently found solution of the Zamolodchikov tetrahedron equation. A projection (from three to two space–time dimensions) property of the solution is used to identify the symmetry of the model at the Mott critical point as , with deformation parameter q = −1. Based on this result, the low-energy effective field theory for the model is obtained and shown to be a lattice double Chern–Simons theory with coupling constant k = 1 (with the standard normalization). By further employing the effective filed theory methods, we show that the Mott transition that arises is of topological nature, with vortices in an antiferromagnetic array and matter currents characterized by a d-density wave order parameter. We also analyze the behavior of the system upon weak coupling, and conclude that it undergoes a quantum gas–liquid transition which belongs to the Ising universality class.     

Bayesian approach to electron correlation in density functional theory

In the present communication we applied the Bayesian conditional probability approach to the wave function of a many‐electron system that resulted in the appearance of a quantum vector potential in the DFT Schrödinger equation due to electron correlation, apart from the correlation energy term. Mathematically, the effect of this vector potential is equivalent to a magnetic field that corresponds in particular to a conservative irrotational one if it is considered in connection with the correlation potential. An analysis of the effect of the correlation momentum on the electronic transitions suggested that the electron correlation increases the transition probability.     

A partitioned density functional theory of freezing: application to soft spheres

A non-perturbative density functional theory (DFT) for inhomogeneous fluids is developed by partitioning the functional into short range (‘entropic’) and long range (‘energetic’) contributions. The short range part is treated using standard weighted density functional techniques and the long range contribution is evaluated exactly. This method, which is a generalization of a method due to Likos, C., and Senatore, G., 1995, J. Phys.: Condens. Matter, 7, 6797, does not require the use of a reference system. Results are presented for the calculation of the crystal-/fluid phase coexistence for systems interacting with inverse-power potentials of the form r ^-n , where n = 4, 6 and 12. These results show that this non-perturbative DFT is capable of predicting the freezing of long range inverse power systems (n = 4, 6) into a body-centredcubic lattice. Improvements over earlier methods also are noted in the current results for the solid structure as measured by the Lindemann ratio.     

A perturbation approach to the density functional theory of adsorption

A modified treatment of an exact density functional theory for non-uniform fluids due to Saam and Ebner is presented and a perturbation method of solution is proposed which avoids the need for a local density approximation. For hard-core fluids near a hard wall the equation for the equilibrium density reduces tothe wall-particle version of the RHNC approximation.     

Density functional theory of single-file classical fluids

An overcomplete density functional formalism is derived to represent the thermal behaviour of confined classical fluids under single-file conditions. Strictly one-dimensional hard rod systems are reanalysed from this viewpoint, and the context is then broadened to encompass hard spheres in cylindrical enclosures. Applications to non-single-file conditions, modulated enclosures, and confined polymers are mentioned.     

苯胺及掺杂态苯胺低聚物结构的密度泛函理论研究

采用基于密度泛函理论的计算方法,研究了苯胺低聚物及盐酸、对甲苯磺酸掺杂苯胺低聚物的几何结构和电子结构.结果表明,质子酸掺杂使苯胺低聚物分子链上醌环中C-C单、双键交替的性质被削弱,同时链间C=N键长明显增大.掺杂位上链间C-N-C键角增大,相邻环间的扭转角减小,分子链的共面性有所改善.与盐酸掺杂对比,对甲苯磺酸掺杂更利于电子从环内向链间转移,理论上可更好地改善聚苯胺材料的导电性能.