Théorie de la perturbation de Møller-Plesset

La théorie de la perturbation de Møller-Plesset (MP) est une des nombreuses méthodes post-Hartree-Fock ab initio en chimie quantique appliquée dans le cadre de la chimie numérique. Elle améliore la méthode de Hartree-Fock en y apportant les effets de corrélation électronique au moyen de la théorie de la perturbation de Rayleigh-Schrödinger (RS-PT) au deuxième (MP2), troisième (MP3) ou quatrième (MP4) ordre habituellement. L'idée principale de cette méthode a été publiée dès 1934. Théorie de la perturbation de Rayleigh-Schrödinger La théorie MP est une application particulière de la théorie de la perturbation de Rayleigh-Schrödinger (en anglais Rayleigh-Schrödinger perturbation theory, RS-PT). Dans la RS-PT, on considère un opérateur hamiltonien non perturbé \hat{H}{0} auquel est ajouté une petite perturbation (parfois externe) \hat{V}: : \hat{H} = \hat{H}{0} + \lambda \hat V , où λ est un paramètre arbitraire réel. Dans la théorie MP

Efficient Treatment of Correlation Energies at the Basis-Set Limit by Monte Carlo Summation of Continuum States

Martin Peter Bircher, Ursula Röthlisberger, Justin Villard

The calculation of electron correlation is vital for the description of atomistic phenomena in physics, chemistry, and biology. However, accurate wavefunction-based methods exhibit steep scaling and often sluggish convergence with respect to the basis set at hand. Because of their delocalization and ease of extrapolation to the basis-set limit, plane waves would be ideally suited for the calculation of basis-set limit correlation energies. However, the routine use of correlated wavefunction approaches in a plane-wave basis set is hampered by prohibitive scaling due to a large number of virtual continuum states and has not been feasible for all but the smallest systems, even if substantial computational resources are available and methods with comparably beneficial scaling, such as the Moller-Plesset perturbation theory to second order (MP2), are used. Here, we introduce a stochastic sampling of the MP2 integrand based on Monte Carlo summation over continuum orbitals, which allows for speedups of up to a factor of 1000. Given a fixed number of sampling points, the resulting algorithm is dominated by a flat scaling of similar to O(N-2). Absolute correlation energies are accurate to

AMER CHEMICAL SOC2020

Cluster perturbation theory. III. Perturbation series for coupled cluster singles and doubles excitation energies

Pablo Jonas Baudin, Jógvan Magnus Olsen

The cluster perturbation series, CPS(D), for coupled cluster singles and doubles excitation energies is considered. It is demonstrated that the second-order model CPS(D-2) is identical to the configuration interaction singles with perturbative doubles, CIS(D) model. The third-order model, CPS(D-3), provides excitation energies of coupled cluster singles and doubles (CCSD) quality in the sense that the difference between CPS(D-3) and CCSD excitation energies is of the same size or smaller than the effect of adding triples corrections to CCSD excitation energies. We further show that the third-order corrections can be efficiently implemented, in particular, when the resolution of the identity approximation is used for integrals. We also show that the CPS(D-3) excitation energies can be determined for system sizes that are far beyond what can be considered in conventional CCSD excitation energy calculations. Published under license by AIP Publishing.

AMER INST PHYSICS2019

Level crossings and chiral transitions in transverse-field Ising models of adatom and Rydberg chains

Ivo Aguiar Maceira

This thesis is motivated by recent experiments on systems described by extensions of the one-dimensional transverse-field Ising (TFI) model where (1) finite-size properties of Ising-ordered phases -- specifically, ground state level crossings -- were observed and (2) continuous phase transitions related to the p-state chiral clock model were probed, with interesting but only partially conclusive results regarding the nature of the phase transitions and the possible existence of a chiral universality class.For (1), the relation of the level crossings to topologically protected edge modes of Majorana fermion models is discussed, and the implication is made explicit that the auto-correlation time of the edge spins may be infinite even for non-integrable albeit finite systems, and independently of temperature. The level crossings are then reinterpreted in the context of degenerate perturbation theory as being a consequence of destructive quantum interference between tunneling processes involving different numbers of spin-flip operations. It is shown that this phenomenon is independent of the lattice geometry, as long as this one is not geometrically frustrated, and is ubiquitous to TFI-like models, being also found in single spin-S systems, the latter having already been observed in the field of magnetic molecules. The effect of disorder on the crossings is studied in lowest order.For (2), we perform density matrix renormalization group simulations on open chains to investigate the experimentally observed quantum phase transitions and we conclude that isolated conformal critical points exist along the p=3 and p=4 critical boundaries: we accurately locate such points and characterize their universality classes by determining critical exponents numerically, where we find that the p=3 agrees with a 3-state Potts universality class and the p=4 point agrees with an Ashkin-Teller universality class with Îœ â 0.80 (Î» â 0.5). Our results are in favor of the existence of chiral transition lines surrounding the conformal points, beyond which a gapless intermediate phase is expected.

EPFL2022

Level crossings and chiral transitions in transverse-field Ising models of adatom and Rydberg chains

Ivo Aguiar Maceira

EPFL2022