arXiv subjects

Samuel Cloutier

Publications and source records attributed to Samuel Cloutier.

3 recordsLinked to original sources

arXiv2022

Near-exact treatment of seniority-zero ground and excited states with a Richardson-Gaudin mean-field

Eigenvectors of the reduced Bardeen-Cooper-Schrieffer Hamiltonian, Richardson-Gaudin (RG) states, are used as a variational wavefunction Ansatz for strongly-correlated electronic systems. These states are geminal products whose coefficients are solutions of non-linear equations. Previous results showed un-physical behaviour but in this contribution it is shown that with only the variational solution for the ground state, all the seniority-zero states are quite well approximated. The difficulty is in choosing the correct RG state. The systems studied showed a clear choice and we expect it should always be possible to reason physically which state to choose.

physics.chem-ph↗

arXiv2020

Transition density matrices of Richardson-Gaudin states

Recently, ground state eigenvectors of the reduced Bardeen-Cooper-Schrieffer Hamiltonian, Richardson-Gaudin (RG) states, have been employed as a wavefunction ansatz for strong correlation. This wavefunction physically represents a mean-field of pairs of electrons (geminals) with a constant pairing strength. To move beyond the mean-field, one must develop the wavefunction in the basis of all the RG states. This requires both practical expressions for transition density matrices and an idea of which states are most important in the expansion. In this contribution, we present expressions for the transition density matrix elements and calculate them numerically for half-filled picket fence models. There are no Slater-Condon rules for RG states, though an analogue of the aufbau principle proves to be useful in choosing which states are important.

physics.chem-ph↗

arXiv2020

Reduced density matrices of Richardson-Gaudin states in the Gaudin algebra basis

Eigenvectors of the reduced Bardeen-Cooper-Schrieffer Hamiltonian have recently been employed as a variational wavefunction ansatz in quantum chemistry. This wavefunction is a mean-field of pairs of electrons (geminals). In this contribution we report optimal expressions for their reduced density matrices in both the original physical basis and the basis of the Richardson-Gaudin pairs. Physical basis expressions were originally reported by Gorohovsky and Bettelheim. In each case, the expressions scale like $\mathcal{O}(N^4)$, with the most expensive step the solution of linear equations. Analytic gradients are also reported in the physical basis. These expressions are an important step towards practical mean-field methods to treat strongly-correlated electrons.

physics.chem-ph↗