S. De Baerdemacker

Eigenvalue-based determinants for scalar products and form factors in Richardson–Gaudin integrable models coupled to a bosonic mode

P. Claeys, S. De Baerdemacker, M. Van Raemdonck, D. Van Neck
Journal of Physics A: Mathematical and Theoretical
48 (42), 425201
2015
A1

Abstract 

Starting from integrable su(2) (quasi-)spin Richardson–Gaudin (RG) XXZ models we derive several properties of integrable spin models coupled to a bosonic mode. We focus on the Dicke–Jaynes–Cummings–Gaudin models and the two-channel (p + ip)-wave pairing Hamiltonian. The pseudo-deformation of the underlying su(2) algebra is here introduced as a way to obtain these models in the contraction limit of different RG models. This allows for the construction of the full set of conserved charges, the Bethe ansatz state, and the resulting RG equations. For these models an alternative and simpler set of quadratic equations can be found in terms of the eigenvalues of the conserved charges. Furthermore, the recently proposed eigenvalue-based determinant expressions for the overlaps and form factors of local operators are extended to these models, linking the results previously presented for the Dicke–Jaynes–Cummings–Gaudin models with the general results for RG XXZ models.

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Polynomial scaling approximations and Dynamic Correlation Corrections to Doubly Occupied Configuration Interaction wave functions

M. Van Raemdonck, D. Alcoba, W. Poelmans, S. De Baerdemacker, A. Torre, L. Lain, G. Massaccesi, D. Van Neck, P. Bultinck
Journal of Chemical Physics
143 (10), 104106
2015
A1

Abstract 

A class of polynomial scaling methods that approximate Doubly Occupied Configuration Interaction (DOCI) wave functions and improve the description of dynamic correlation is introduced. The accuracy of the resulting wave functions is analysed by comparing energies and studying the overlap between the newly developed methods and full configuration interaction wave functions, showing that a low energy does not necessarily entail a good approximation of the exact wave function. Due to the dependence of DOCI wave functions on the single-particle basis chosen, several orbital optimisation algorithms are introduced. An energy-based algorithm using the simulated annealing method is used as a benchmark. As a computationally more affordable alternative, a seniority number minimising algorithm is developed and compared to the energy based one revealing that the seniority minimising orbital set performs well. Given a well-chosen orbital basis, it is shown that the newly developed DOCI based wave functions are especially suitable for the computationally efficient description of static correlation and to lesser extent dynamic correlation.

Open Access version available at UGent repository

Variational optimization of the second order density matrix corresponding to a seniority-zero configuration interaction wave function

W. Poelmans, M. Van Raemdonck, B. Verstichel, S. De Baerdemacker, A. Torre, L. Lain, G. Massaccesi, D. Alcoba, P. Bultinck, D. Van Neck
Journal of Chemical Theory and Computation (JCTC)
11 (9), 4064–4076
2015
A1

Abstract 

We perform a direct variational determination of the second-order (two-particle) density matrix corresponding to a many-electron system, under a restricted set of the two-index $N$-representability $\mathcal{P}$-, $\mathcal{Q}$-, and $\mathcal{G}$-conditions. In addition, we impose a set of necessary constraints that the two-particle density matrix must be derivable from a doubly-occupied many-electron wave function, i.e.\ a singlet wave function for which the Slater determinant decomposition only contains determinants in which spatial orbitals are doubly occupied. We rederive the two-index $N$-representability conditions first found by Weinhold and Wilson and apply them to various benchmark systems (linear hydrogen chains, He, $\text{N}_2$ and $\text{CN}^-$). This work is motivated by the fact that a doubly-occupied many-electron wave function captures in many cases the bulk of the static correlation. Compared to the general case, the structure of doubly-occupied two-particle density matrices causes the associate semidefinite program to have a very favorable scaling as $L^3$, where $L$ is the number of spatial orbitals. Since the doubly-occupied Hilbert space depends on the choice of the orbitals, variational calculation steps of the two-particle density matrix are interspersed with orbital-optimization steps (based on Jacobi rotations in the space of the spatial orbitals). We also point to the importance of symmetry breaking of the orbitals when performing calculations in a doubly-occupied framework.

The Dicke model as the contraction limit of a pseudo-deformed Richardson-Gaudin model

P. Claeys, S. De Baerdemacker, M. Van Raemdonck, D. Van Neck
Journal of Physics Conference Series
597, UNSP 012025
2015
P1

Abstract 

The Dicke model is derived in the contraction limit of a pseudo-deformation of the quasispin algebra in the su(2)-based Richardson-Gaudin models. Likewise, the integrability of the Dicke model is established by constructing the full set of conserved charges, the form of the Bethe Ansatz state, and the associated Richardson-Gaudin equations. Thanks to the formulation in terms of the pseudo-deformation, the connection from the su(2)-based Richardson-Gaudin model towards the Dicke model can be performed adiabatically.

Open Access version available at UGent repository

CheMPS2: Improved DMRG-SCF routine and correlation functions

S. Wouters, W. Poelmans, S. De Baerdemacker, P.W. Ayers, D. Van Neck
Computer Physics Communications
191, 235-237
2015
A1

Abstract 

CheMPS2, our spin-adapted implementation of the density matrix renormalization group (DMRG) for ab initio quantum chemistry (Wouters et al., 2014), has several new features. A speed-up of the augmented Hessian Newton–Raphson DMRG self-consistent field (DMRG-SCF) routine is achieved with the direct inversion of the iterative subspace (DIIS). For extended molecules, the active space orbitals can be localized by maximizing the Edmiston–Ruedenberg cost function. These localized orbitals can be ordered according to the topology of the molecule by approximately minimizing the bandwidth of the exchange matrix with the Fiedler vector. The electronic structure can be analyzed by means of the two-orbital mutual information, spin, spin-flip, density, and singlet diradical correlation functions.

Eigenvalue-based method and form-factor determinant representations for integrable XXZ Richardson-Gaudin models

P. Claeys, S. De Baerdemacker, M. Van Raemdonck, D. Van Neck
Physical Review B
91 (15), 155102
2015
A1

Abstract 

We propose an extension of the numerical approach for integrable Richardson-Gaudin models based on a new set of eigenvalue-based variables [A. Faribault et al., Phys. Rev. B 83, 235124 (2011); O. El Araby et al., Phys. Rev. B 85, 115130 (2012)]. Starting solely from the Gaudin algebra, the approach is generalized towards the full class of XXZ Richardson-Gaudin models. This allows for a fast and robust numerical determination of the spectral properties of these models, avoiding the singularities usually arising at the so-called singular points. We also provide different determinant expressions for the normalization of the Bethe ansatz states and form factors of local spin operators, opening up possibilities for the study of larger systems, both integrable and nonintegrable. These expressions can be written in terms of the new set of variables and generalize the results previously obtained for rational Richardson-Gaudin models [A. Faribault and D. Schuricht, J. Phys. A 45, 485202 (2012)] and Dicke-Jaynes-Cummings-Gaudin models [H. Tschirhart and A. Faribault,  J. Phys. A 47, 405204 (2014)]. Remarkably, these results are independent of the explicit parametrization of the Gaudin algebra, exposing a universality in the properties of Richardson-Gaudin integrable systems deeply linked to the underlying algebraic structure.

Open Access version available at UGent repository

Probing pairing correlations in Sn isotopes using Richardson-Gaudin integrability

S. De Baerdemacker, V. Hellemans, R. van den Berg, J.-S. Caux, K. Heyde, M. Van Raemdonck, D. Van Neck, P.A. Johnson, A. Buekenhoudt
Journal of Physics: Conference series
533, 012058
2014
P1

Abstract 

Pairing correlations in the even-even A = 102 − 130 Sn isotopes are discussed, based on the Richardson-Gaudin variables in an exact Woods-Saxon plus reduced BCS pairing framework. The integrability of the model sheds light on the pairing correlations, in particular on the previously reported sub-shell structure.

Open Access version available at UGent repository

Scaling a Unitary Matrix

A. De Vos (Alexis), S. De Baerdemacker
Open Systems & Information Dynamics
21 (4), 1450013
2014
A1

Abstract 

The iterative method of Sinkhorn allows, starting from an arbitrary real matrix with non-negative entries, to find a so-called 'scaled matrix' which is doubly stochastic, i.e. a matrix with all entries in the interval (0, 1) and with all line sums equal to 1. We conjecture that a similar procedure exists, which allows, starting from an arbitrary unitary matrix, to find a scaled matrix which is unitary and has all line sums equal to 1. The existence of such algorithm guarantees a powerful decomposition of an arbitrary quantum circuit.

Matrix Calculus for Classical and Quantum Circuits

A. De Vos (Alexis), S. De Baerdemacker
ACM Journal on Emerging Technologies in Computing Systems (JETC)
11 (2), 9
2014
A1

Abstract 

Quantum computation on w qubits is represented by the infinite unitary group U(2(w)); classical reversible computation on w bits is represented by the finite symmetric group S-2w. In order to establish the relationship between classical reversible computing and quantum computing, we introduce two Lie subgroups XU(n) and ZU(n) of the unitary group U(n). The former consists of all unitary n x n matrices with all line sums equal to 1; the latter consists of all unitary diagonal n x n matrices with first entry equal to 1. Such a group structure also reveals the relationship between matrix calculus and diagrammatic zx-calculus of quantum circuits.

Non-Variational Orbital Optimization Techniques for the AP1roG Wave Function

K. Boguslawski, P. Tecmer, P.W. Ayers, P. Bultinck, S. De Baerdemacker, D. Van Neck
Journal of Chemical Theory and Computation (JCTC)
10 (11), 4873-4882
2014
A1

Abstract 

We introduce new nonvariational orbital optimization schemes for the antisymmetric product of one-reference orbital geminal (AP1roG) wave function (also known as pair-coupled cluster doubles) that are extensions to our recently proposed projected seniority-two (PS2-AP1roG) orbital optimization method [ J. Chem. Phys. 2014, 140, 214114)]. These approaches represent less stringent approximations to the PS2-AP1roG ansatz and prove to be more robust approximations to the variational orbital optimization scheme than PS2-AP1roG. The performance of the proposed orbital optimization techniques is illustrated for a number of well-known multireference problems: the insertion of Be into H2, the automerization process of cyclobutadiene, the stability of the monocyclic form of pyridyne, and the aromatic stability of benzene.

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