arXiv subjects

P. W. Ayers

Publications and source records attributed to P. W. Ayers.

3 recordsLinked to original sources

arXiv2020

Richardson-Gaudin mean-field for strong correlation in quantum chemistry

Ground state eigenvectors of the reduced Bardeen-Cooper-Schrieffer Hamiltonian are employed as a wavefunction ansatz to model strong electron correlation in quantum chemistry. This wavefunction is a product of weakly-interacting pairs of electrons. While other geminal wavefunctions may only be employed in a projected Schrödinger equation, the present approach may be solved variationally with polynomial cost. The resulting wavefunctions are used to compute expectation values of Coulomb Hamiltionans and we present results for atoms and dissociation curves which are in agreement with doubly-occupied configuration interaction (DOCI) data. The present approach will serve as the starting point for a many-body theory of pairs, much as Hartree-Fock is the starting point for weakly-correlated electrons.

physics.chem-ph↗

arXiv2009

On the thermodynamical analogy in spin-polarized density functional theory

The thermodynamical analogy of density functional theory, which is an organic part of the spin-independent version of the theory, is reconsidered for its spin-polarized generalization in view of the recently uncovered nonuniqueness of the external magnetic field B(r) corresponding to a given pair of density n(r) and spin density n_s(r). For ground states, the nonuniqueness of B(r) implies the nondifferentiability of the energy functional E[n,n_s] with respect to n_s(r). It is shown, on the other hand, that this nonuniqueness allows the existence of the one-sided derivatives of E[n,n_s] with respect to n_s(r). Although the N-electron ground state can always be obtained from the minimization of E[n,n_s] without any constraint on the spin number N_s, the Lagrange multiplier mu_s associated with the fixation of N_s does not vanish even for ground states. Rather, mu_s is identified as the left- or right-side derivative of the total energy with respect to N_s. This justifies the interpretation of mu_s as a (spin) chemical potential, which is the cornerstone of the thermodynamical analogy.

physics.chem-ph↗

arXiv2006

Quasiparticle properties in a density functional framework

We propose a framework to construct the ground-state energy and density matrix of an N-electron system by solving selfconsistently a set of single-particle equations. The method can be viewed as a non-trivial extension of the Kohn-Sham scheme (which is embedded as a special case). It is based on separating the Green's function into a quasi-particle part and a background part, and expressing only the background part as a functional of the density matrix. The calculated single-particle energies and wave functions have a clear physical interpretation as quasiparticle energies and orbitals.

physics.chem-ph↗