Related papers: Natural occupation numbers: When do they vanish?
The strong boundary normalized condition of wavefunction for fully occupied semicore 3d orbitals leads the linear response DFT+U on such metal oxide to have an insurmountable obstacle in Hubbard U determination. We treated the orbital…
We derive an equation for the time evolution of the natural occupation numbers for fermionic systems with more than two electrons. The evolution of such numbers is connected with the symmetry-adapted generalized Pauli exclusion principle,…
We study the equilibrium statistical mechanics of classical two-dimensional Coulomb systems living on a pseudosphere (an infinite surface of constant negative curvature). The Coulomb potential created by one point charge exists and goes to…
Explicitly orbital-dependent approximations to the exchange-correlation energy functional of density functional theory typically not only depend on the single-particle Kohn-Sham orbitals but also on their occupation numbers in the ground…
A novel approach is suggested for the statistical description of quantum systems of interacting particles. The key point of this approach is that a typical eigenstate in the energy representation (shape of eigenstates, SE) has a well…
Fractional occupation numbers can produce open-shell degeneracy in density functional theory. We develop the corresponding perturbation theory by requiring that a differentiable map connects the initial and perturbed states. The degenerate…
Students in quantum mechanics class are taught that the wave function contains all knowable information about an isolated system. Later in the course, this view seems to be contradicted by the mysterious density matrix, which introduces a…
We investigate the suitability of natural orbitals as a basis for describing many-body excitations. We analyze to which extend the natural orbitals describe both bound as well as ionized excited states and show that depending on the…
Functionals that strive to correct for such self-interaction errors, such as those obtained by imposing the Perdew-Zunger self-interaction correction or the generalized Koopmans' condition, become orbital dependent or orbital-density…
Functionals that explicitly depend on occupied, unoccupied, or fractionally-occupied orbitals are rigorously formalized using Clifford algebras, and a variational principle is established that facilitates orbital (and occupation)…
Natural orbital functional theory is considered for systems with one or more unpaired electrons. An extension of the Piris natural orbital functional (PNOF) based on electron pairing approach is presented, specifically, we extend the…
Given a vector space of microscopic quantum observables, density functional theory is formulated on its dual space. A generalized Hohenberg-Kohn theorem and the existence of the universal energy functional in the dual space are proven. In…
The probability operator is derived from first principles for an equilibrium quantum system. It is also shown that the superposition states collapse into a mixture of states giving the conventional von Neumann trace form for the quantum…
The relationship between natural orbitals, one-body coherences and two-body correlations is explored for bosonic many-body systems of definite parity with two occupied single-particle states. We show that the strength of local two-body…
The analytic energy gradients in the atomic orbital representation have recently been published (J. Chem. Phys. 146, 014102, 2017) within the framework of the natural orbital functional theory (NOFT). We provide here an alternative…
We study statistical properties of $N$ non-interacting identical bosons or fermions in the canonical ensemble. We derive several general representations for the $p$-point correlation function of occupation numbers $\overline{n_1\cdots…
Quantum mechanical scalar particle with polarizability is considered in the presence of the Coulomb field. Separation of variables is performed with the use of Wigner $D$-functions, the radial system of 15 equations is reduced to a single…
Based on recent progress on fermionic exchange symmetry we propose a way to develop new functionals for reduced density matrix functional theory. For some settings with an odd number of electrons, by assuming saturation of the inequalities…
The Wigner-Weyl transform and phase space formulation of a density matrix approach are applied to a non-Hermitian model which is quadratic in positions and momenta. We show that in the presence of a quantum environment or reservoir, mean…
The leading terms in the large-$R$ asymptotics of the functional of the one-electron reduced density matrix for the ground-state energy of the H$_2$ molecule with the internuclear separation $R$ is derived thanks to the solution of the…