B. Verstichel

Projector quantum Monte Carlo with matrix product states

S. Wouters, B. Verstichel, D. Van Neck, G. K.-L. Chan
Physical Review B
90, 045104
2014
A1

Abstract 

We marry tensor network states (TNS) and projector quantum Monte Carlo (PMC) to overcome the high computational scaling of TNS and the sign problem of PMC. Using TNS as trial wavefunctions provides a route to systematically improve the sign structure and to eliminate the bias in fixed-node and constrained-path PMC. As a specific example, we describe phaseless auxiliary-field quantum Monte Carlo with matrix product states (MPS-AFQMC). MPS-AFQMC improves significantly on the DMRG ground-state energy. For the J1-J2 model on two-dimensional square lattices, we observe with MPS-AFQMC an order of magnitude reduction in the error for all couplings, compared to DMRG. The improvement is independent of walker bond dimension, and we therefore use bond dimension one for the walkers. The computational cost of MPS-AFQMC is then quadratic in the bond dimension of the trial wavefunction, which is lower than the cubic scaling of DMRG. The error due to the constrained-path bias is proportional to the variational error of the trial wavefunction. We show that for the J1-J2 model on two-dimensional square lattices, a linear extrapolation of the MPS-AFQMC energy with the discarded weight from the DMRG calculation allows to remove the constrained-path bias. Extensions to other tensor networks are briefly discussed.

Variational optimization of the 2DM: approaching three-index accuracy using extended cluster constraints

B. Verstichel, W. Poelmans, S. De Baerdemacker, S. Wouters, D. Van Neck
The European Physical Journal B
87(3), 59
2014
A1

Abstract 

The reduced density matrix is variationally optimized for the two-dimensional Hubbard model. Exploiting all symmetries present in the system, we have been able to study 6 × 6 lattices at various fillings and different values for the on-site repulsion, using the highly accurate but computationally expensive three-index conditions. To reduce the computational cost we study the performance of imposing the three-index constraints on local clusters of 2 × 2 and 3 × 3 sites. We subsequently derive new constraints which extend these cluster constraints to incorporate the open-system nature of a cluster on a larger lattice. The feasibility of implementing these new constraints is demonstrated by performing a proof-of-principle calculation on the 6 × 6 lattice. It is shown that a large portion of the three-index result can be recovered using these extended cluster constraints, at a fraction of the computational cost.

Extended random phase approximation method for atomic excitation energies from correlated and variationally optimized second-order density matrices

H. van Aggelen, B. Verstichel, G. Acke, M. Degroote, P. Bultinck, P.W. Ayers, D. Van Neck
Computational and Theoretical Chemistry
1003 (2013), 50-54
2013
A1

The sharp-G N-representability condition

P.A. Johnson, P.W. Ayers, B. Verstichel, D. Van Neck, H. van Aggelen
Computational and Theoretical Chemistry
1003 (2013), 32-36
2013
A1

Abstract 

The G-condition for the N-representability of the two-electron reduced density matrix is tightened by replacing the semidefiniteness constraint with the true upper and lower bounds of the G-type Hamiltonian operator. The lower bound is not easily computed (in contrast to the sharp P- and Q-conditions), but maps onto a well-known integer programming problem. The sharp-G, sharp-P, and sharp-Q conditions are just three members of a much broader class of conditions based on exactly solvable model Hamiltonians.

Extensive v2DM study of the one-dimensional Hubbard model for large lattice sizes: Exploiting translational invariance and parity

B. Verstichel, H. van Aggelen, W. Poelmans, S. Wouters, D. Van Neck
Computational and Theoretical Chemistry
1003 (2013), 12-21
2013
A1

Abstract 

Using variational density matrix optimization with two- and three-index conditions we study the one-dimensional Hubbard model with periodic boundary conditions at various filling factors. Special attention is directed to the full exploitation of the available symmetries, more specifically the combination of translational invariance and space-inversion parity, which allows for the study of large lattice sizes. We compare the computational scaling of three different semidefinite programming algorithms with increasing lattice size, and find the boundary point method to be the most suited for this type of problem. Several physical properties, such as the two-particle correlation functions, are extracted to check the physical content of the variationally determined density matrix. It is found that the three-index conditions are needed to correctly describe the full phase diagram of the Hubbard model. We also show that even in the case of half filling, where the ground-state energy is close to the exact value, other properties such as the spin-correlation function can be flawed.

Open Access version available at UGent repository

Variational two-particle density matrix calculation for the Hubbard model below half filling using spin-adapted lifting conditions

B. Verstichel, H. van Aggelen, W. Poelmans, D. Van Neck
Physical Review Letters
108 (21), 213001
2012
A1

Abstract 

The variational determination of the two-particle density matrix is an interesting, but not yet fully explored technique that allows to obtain ground-state properties of a quantum many-body system without reference to an N-particle wave function. The one-dimensional fermionic Hubbard model has been studied before with this method, using standard two- and three-index conditions on the density matrix [J. R. Hammond et al., Phys. Rev. A 73, 062505 (2006)], while a more recent study explored so-called subsystem constraints [N. Shenvi et al., Phys. Rev. Lett. 105, 213003 (2010)]. These studies reported good results even with only standard two-index conditions, but have always been limited to the half-filled lattice. In this Letter we establish the fact that the two-index approach fails for other fillings. In this case, a subset of three-index conditions is absolutely needed to describe the correct physics in the strong-repulsion limit. We show that applying lifting conditions [J.R. Hammond et al., Phys. Rev. A 71, 062503 (2005)] is the most economical way to achieve this, while still avoiding the computationally much heavier three-index conditions. A further extension to spin-adapted lifting conditions leads to increased accuracy in the intermediate repulsion regime. At the same time we establish the feasibility of such studies to the more complicated phase diagram in two-dimensional Hubbard models.

Open Access version available at UGent repository

Considerations on describing non-singlet spin states in variational second order density matrix methods

H. van Aggelen, B. Verstichel, P. Bultinck, D. Van Neck, P.W. Ayers
Journal of Chemical Physics
136, 014110
2012
A1

Abstract 

Despite the importance of non-singlet molecules in chemistry, most variational second order density matrix calculations have focused on singlet states. Ensuring that a second order density matrix is derivable from a proper N-electron spin state is a difficult problem because the second order density matrix only describes one- and two-particle interactions. In pursuit of a consistent description of spin in second order density matrix theory, we propose and evaluate two main approaches: we consider constraints derived from a pure spin state and from an ensemble of spin states. This paper makes a comparative assessment of the different approaches by applying them to potential energy surfaces for different spin states of the oxygen and carbon dimer. We observe two major shortcomings of the applied spin constraints: they are not size consistent and they do not reproduce the degeneracy of the different states in a spin multiplet. First of all, the spin constraints are less strong when applied to a dissociated molecule than when they are applied to the dissociation products separately. Although they impose correct spin expectation values on the dissociated molecule, the dissociation products do not have correct spin expectation values. Secondly, both under “pure spin state conditions” and under “ensemble spin state” conditions is the energy a convex function of the spin projection. Potential energy surfaces for different spin projections of the same spin state may give a completely different picture of the molecule's bonding. The maximal spin projection always gives the most strongly constrained energy, but is also significantly more expensive to compute than a spin-averaged ensemble. In the dissociation limit, both the problem of nondegeneracy of equivalent spin projections, size-inconsistency and unphysical dissociation can be corrected by means of subspace energy constraints.

Variational determination of the second-order density matrix for the isoelectronic series of beryllium, neon, and silicon

B. Verstichel, H. van Aggelen, D. Van Neck, P.W. Ayers, P. Bultinck
Physical Review A
80 (3), 032508
2009
A1

Abstract 

The isoelectronic series of Be, Ne and Si are investigated using a variational determination of the second-order density matrix. A semidefinite program was developed that exploits all rotational and spin symmetries in the atomic system. We find that the method is capable of describing the strong static electron correlations due to the incipient degeneracy in the hydrogenic spectrum for increasing central charge. Apart from the ground-state energy various other properties are extracted from the variationally determined second-order density matrix. The ionization energy is constructed using the extended Koopmans' theorem. The natural occupations are also studied, as well as the correlated Hartree-Fock-like single particle energies. The exploitation of symmetry allows to study the basis set dependence and results are presented for correlation-consistent polarized valence double, triple and quadruple zeta basis sets.

Open Access version available at UGent repository

Incorrect diatomic dissociation in variational reduced density matrix theory arises from the flawed description of fractionally charged atoms

H. van Aggelen, P. Bultinck, B. Verstichel, D. Van Neck, P.W. Ayers
Physical Chemistry Chemical Physics (PCCP)
11 (27), 5558-5560
2009
A1

Abstract 

The behaviour of diatomic molecules is examined using the variational second-order density matrix method under the P, Q and G conditions. It is found that the method describes the dissociation limit incorrectly, with fractional charges on the well-separated atoms. This can be traced back to the behaviour of the energy versus the number of electrons for the isolated atoms. It is shown that the energies for fractional charges are much too low.

Chemical verification of variational second-order density matrix based potential energy surfaces for the N2 isoelectronic series

H. van Aggelen, B. Verstichel, P. Bultinck, D. Van Neck, P.W. Ayers, D.L. Cooper
Journal of Chemical Physics
132, 114112
2010
A1

Abstract 

A variational optimization of the second-order density matrix under the P-, Q-, and G-conditions was carried out for a set of diatomic 14-electron molecules, including N2, O22+, NO+, CO, and CN−. The dissociation of these molecules is studied by analyzing several chemical properties (dipole moments, population analysis, and bond indices) up to the dissociation limit (10 and 20 Å). Serious chemical flaws are observed for the heteronuclear diatomics in the dissociation limit. A careful examination of the chemical properties reveals that the origin of the dissociation problem lies in the flawed description of fractionally occupied species under the P-, Q-, and G-conditions. A novel constraint is introduced that imposes the correct dissociation and enforces size consistency. The effect of this constraint is illustrated with calculations on NO+, CO, CN−, N2, and O22+.

Open Access version available at UGent repository

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