28 research outputs found
Ground-state properties of the spin-1/2 antiferromagnetic Heisenberg model on the triangular lattice: A variational study based on entangled-plaquette states
We study, on the basis of the general entangled-plaquette variational ansatz,
the ground-state properties of the spin-1/2 antiferromagnetic Heisenberg model
on the triangular lattice. Our numerical estimates are in good agreement with
available exact results and comparable, for large system sizes, to those
computed via the best alternative numerical approaches, or by means of
variational schemes based on specific (i.e., incorporating problem dependent
terms) trial wave functions. The extrapolation to the thermodynamic limit of
our results for lattices comprising up to N=324 spins yields an upper bound of
the ground-state energy per site (in units of the exchange coupling) of
[ for the XX model], while the estimated
infinite-lattice order parameter is (i.e., approximately 64% of the
classical value).Comment: 8 pages, 3 tables, 2 figure
Correct quantum chemistry in a minimal basis from effective Hamiltonians
We describe how to create ab-initio effective Hamiltonians that qualitatively
describe correct chemistry even when used with a minimal basis. The
Hamiltonians are obtained by folding correlation down from a large parent basis
into a small, or minimal, target basis, using the machinery of canonical
transformations. We demonstrate the quality of these effective Hamiltonians to
correctly capture a wide range of excited states in water, nitrogen, and
ethylene, and to describe ground and excited state bond-breaking in nitrogen
and the chromium dimer, all in small or minimal basis sets
Mechanical Control of Spin States in Spin-1 Molecules and the Underscreened Kondo Effect
The ability to make electrical contact to single molecules creates
opportunities to examine fundamental processes governing electron flow on the
smallest possible length scales. We report experiments in which we controllably
stretch individual cobalt complexes having spin S = 1, while simultaneously
measuring current flow through the molecule. The molecule's spin states and
magnetic anisotropy were manipulated in the absence of a magnetic field by
modification of the molecular symmetry. This control enabled quantitative
studies of the underscreened Kondo effect, in which conduction electrons only
partially compensate the molecular spin. Our findings demonstrate a mechanism
of spin control in single-molecule devices and establish that they can serve as
model systems for making precision tests of correlated-electron theories.Comment: main text: 5 pages, 4 figures; supporting information attached; to
appear in Science
Excited-state calculations with quantum Monte Carlo
Quantum Monte Carlo methods are first-principle approaches that approximately
solve the Schr\"odinger equation stochastically. As compared to traditional
quantum chemistry methods, they offer important advantages such as the ability
to handle a large variety of many-body wave functions, the favorable scaling
with the number of particles, and the intrinsic parallelism of the algorithms
which are particularly suitable to modern massively parallel computers. In this
chapter, we focus on the two quantum Monte Carlo approaches most widely used
for electronic structure problems, namely, the variational and diffusion Monte
Carlo methods. We give particular attention to the recent progress in the
techniques for the optimization of the wave function, a challenging and
important step to achieve accurate results in both the ground and the excited
state. We conclude with an overview of the current status of excited-state
calculations for molecular systems, demonstrating the potential of quantum
Monte Carlo methods in this field of applications
New Strategies in Modeling Electronic Structures and Properties with Applications to Actinides
This chapter discusses contemporary quantum chemical methods and provides
general insights into modern electronic structure theory with a focus on
heavy-element-containing compounds. We first give a short overview of
relativistic Hamiltonians that are frequently applied to account for
relativistic effects. Then, we scrutinize various quantum chemistry methods
that approximate the -electron wave function. In this respect, we will
review the most popular single- and multi-reference approaches that have been
developed to model the multi-reference nature of heavy element compounds and
their ground- and excited-state electronic structures. Specifically, we
introduce various flavors of post-Hartree--Fock methods and optimization
schemes like the complete active space self-consistent field method, the
configuration interaction approach, the Fock-space coupled cluster model, the
pair-coupled cluster doubles ansatz, also known as the antisymmetric product of
1 reference orbital geminal, and the density matrix renormalization group
algorithm. Furthermore, we will illustrate how concepts of quantum information
theory provide us with a qualitative understanding of complex electronic
structures using the picture of interacting orbitals. While modern quantum
chemistry facilitates a quantitative description of atoms and molecules as well
as their properties, concepts of quantum information theory offer new
strategies for a qualitative interpretation that can shed new light onto the
chemistry of complex molecular compounds.Comment: 43 pages, 3 figures, Version of Recor
Communication: Variation after response in quantum Monte Carlo
We present a new method for modeling electronically excited states that overcomes a key failing of linear response theory by allowing the underlying ground state ansatz to relax in the presence of an excitation. The method is variational, has a cost similar to ground state variational Monte Carlo, and admits both open and periodic boundary conditions. We present preliminary numerical results showing that, when paired with the Jastrow antisymmetric geminal power ansatz, the variation-after-response formalism delivers accuracies for valence and charge transfer single excitations on par with equation of motion coupled cluster, while surpassing coupled cluster's accuracy for excitations with significant doubly excited character
Quantum Monte Carlo Treatment of the Charge Transfer and Diradical Electronic Character in a Retinal Chromophore Minimal Model
The penta-2,4-dieniminium cation (PSB3) displays similar ground state and first excited state potential energy features as those of the retinal protonated Schiff base (RPSB) chromophore in rhodopsin. Recently, PSB3 has been used to benchmark several electronic structure methods, including highly correlated multireference wave function approaches, highlighting the necessity to accurately describe the electronic correlation in order to obtain reliable properties even along the ground state (thermal) isomerization paths. In this work, we apply two quantum Monte Carlo approaches, the variational Monte Carlo and the lattice regularized diffusion Monte Carlo, to study the energetics and electronic properties of PSB3 along representative minimum energy paths and scans related to its thermal cis-trans isomerization. Quantum Monte Carlo is used in combination with the Jastrow antisymmetrized geminal power ansatz, which guarantees an accurate and balanced description of the static electronic correlation thanks to the multiconfigurational nature of the antisymmetrized geminal power term, and of the dynamical correlation, due to the presence of the Jastrow factor explicitly depending on electron-electron distances. Along the two ground state isomerization minimum energy paths of PSB3, CASSCF calculations yield wave functions having either charge transfer or diradical character in proximity of the two transition state configurations. Here, we observe that at the quantum Monte Carlo level of theory, only the transition state with charge transfer character can be located. The conical intersection, which becomes highly sloped, is observed only if the path connecting the two original CASSCF transition states is extended beyond the diradical one, namely by increasing the bond-length-alternation (BLA). These findings are in good agreement with the results obtained by MRCISD+Q calculations, and they demonstrate the importance of having an accurate description of the static and dynamical correlation when studying isomerization and transition states of conjugated systems