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Paul A. Johnson

Publications and source records attributed to Paul A. Johnson.

At least 19 recordsLinked to original sources
arXiv2026

Richardson-Gaudin states of non-zero seniority III: The Perfect-Pairing limit

Strongly correlated electrons can be treated with a configuration interaction of Slater determinants grouped by number of unpaired electrons with exponential cost. The first two papers in this series demonstrated that single reference methods built from Richardson-Gaudin states gave results of similar quality at polynomial cost. In this contribution, the states are simplified substantially yielding the perfect-pairing state as a reference along with its low-lying excitations. The states are much simpler, the computational cost is substantially reduced, and there is no sacrifice in numerical accuracy. Second-order Epstein-Nesbet perturbative corrections for the valence electrons are similar in quality to the complete active space self-consistent field.

physics.chem-ph↗
arXiv2025

Connections between Richardson-Gaudin States, Perfect-Pairing, and Pair Coupled-Cluster Theory

Slater determinants underpin most electronic structure methods, but orbital-based approaches often struggle to describe strong correlation efficiently. Geminal-based theories, by contrast, naturally capture static correlation in bond-breaking and multireference problems, though at the expense of implementation complexity and limited treatment of dynamic effects. In this work, we examine the interplay between orbital and geminal frameworks, focusing on perfect-pairing (PP) wavefunctions and their relation to pair coupled-cluster doubles (pCCD) and Richardson-Gaudin (RG) states. We show that PP arises as an eigenvector of a simplified reduced Bardeen-Cooper-Schrieffer (BCS) Hamiltonian expressed in bonding/antibonding orbital pairs, with the complementary eigenvectors enabling a systematic treatment of weak correlation. Second-order Epstein-Nesbet perturbation theory on top of PP is found to yield energies nearly equivalent to pCCD. These results clarify the role of pair-based ansätze and open avenues for hybrid approaches that combine the strengths of orbital- and geminal-based methods.

physics.chem-ph↗
arXiv2025

Richardson-Gaudin states of non-zero seniority I: matrix elements

Seniority-zero wavefunctions describe bond-breaking processes qualitatively. As eigenvectors of a model Hamiltonian, Richardson-Gaudin states provide a clear physical picture and allow for systematic improvement via standard single reference approaches. Until now, this treatment has been done in the seniority-zero channel. In this manuscript, the corresponding states with higher seniorities are identified, and their couplings through the Coulomb Hamiltonian are computed. In every case, the couplings between the states are computed from the cofactors of their effective overlap matrix. Proof of principle calculations demonstrate that a single reference configuration interaction is comparable with seniority-based configuration interaction computations at a substantially reduced cost. The next manuscript in this series will identify the corresponding Slater-Condon rules and make the computations feasible.

physics.chem-ph↗
arXiv2024

Singlet Geminal Wavefunctions

Wavefunction forms based on products of electron pairs are usually constructed as closed-shell singlets, which is insufficient when the molecular state has a nonzero spin or when the chemistry is determined by $d$- or $f-$electrons. A set of two-electron forms are considered as explicit couplings of second-quantized operators to open-shell singlets. Geminal wavefunctions are constructed and their structure is elaborated. Numerical results for small model systems clearly demonstrate improvement over closed-shell singlet pairs.

physics.chem-ph↗
arXiv2024

Beyond a Richardson-Gaudin mean-field: Slater-Condon rules and perturbation theory

Richardson-Gaudin states provide a basis of the Hilbert space for strongly correlated electrons. In this study, optimal expressions for the transition density matrix elements between Richardson-Gaudin states are obtained with a cost comparable with the corresponding reduced density matrix elements. Analogues of the Slater-Condon rules are identified based on the number of near-zero singular values of the RG state overlap matrix. Finally, a perturbative approach is shown to be close in quality to a configuration interaction of Richardson-Gaudin states while being feasible to compute.

physics.chem-ph↗
arXiv2023

Single reference treatment of strongly correlated H$_4$ and H$_{10}$ isomers with Richardson-Gaudin states

Richardson-Gaudin (RG) states are employed as a variational wavefunction ansatz for strongly correlated isomers of H$_4$ and H$_{10}$. In each case a single RG state describes the seniority-zero sector quite well. Simple natural orbital functionals offer a cheap and reasonable approximation of the outstanding weak correlation in the seniority-zero sector, while systematic improvement is achieved by performing a configuration interaction (CI) in terms of RG states. Other pair theories (e.g. generalized valence bond and pair-coupled-cluster doubles) can provide a good description of many of the geometries considered, but, at short distances, the wavefunctions for the 2D and 3D structures of H$_{10}$ take the form of an RG state that cannot be described by these other theories.

physics.chem-ph↗
arXiv2022

Shear-wave-induced softening and simultaneous compaction in dense granular media through acoustic lubrication at flow heterogeneities

We report the simultaneous softening and compaction of a confined dense granular pack in acoustic resonance experiments. Elastic softening is manifested by a reduction of the shear-wave speed, as the wave amplitude increases beyond some threshold. No macroscopic rearrangement of grains or dilatancy is observed; instead, elastic softening is accompanied by a tiny amount of compaction on the scale of grain asperities. We explain these apparent contradictory observations using a theoretical model, based on shear transformation zones (STZs), of soft spots and slipping contacts. It predicts a linear shear stress-strain response with negligible macro-plastic deformation due to the small-amplitude acoustic oscillation. However, these waves reduce the interparticle friction and contact stiffness through the acoustic lubrication of grain contacts, resulting in an increase in the structural disorder or compactivity and softening of dynamic modulus. The compaction associated with this microscopic friction decrease is consistent with the prediction by an Ising-like correlation between STZs in the subyield regime.

cond-mat.soft↗
arXiv2022

Reduced Density Matrices / Static Correlation Functions of Richardson-Gaudin States Without Rapidities

Seniority-zero geminal wavefunctions are known to capture bond-breaking correlation. Among this class of wavefunctions, Richardson-Gaudin states stand out as they are eigenvectors of a model Hamiltonian. This provides a clear physical picture, clean expressions for reduced density matrix (RDM) elements, and systematic improvement (with a complete set of eigenvectors). Known expressions for the RDM elements require the computation of rapidities, which are obtained by first solving for the so-called eigenvalue based variables (EBV) then root-finding of a Lagrange interpolation polynomial. In this manuscript we obtain expressions for the RDM elements directly in terms of the EBV. The final expressions can be computed with the same cost as the rapidity expressions. Therefore, except in particular circumstances, it is entirely unnecessary to compute rapidities at all. The RDM elements require numerically inverting a matrix and while this is usually undesirable we demonstrate that it is stable, except when there is degeneracy in the single-particle energies. In such cases a different construction would be required.

physics.chem-ph↗
arXiv2022

Bivariational Principle for an Antisymmetrized Product of Nonorthogonal Geminals Appropriate for Strong Electron Correlation

We develop a bivariational principle for an antisymmetric product of nonorthogonal geminals. Special cases reduce to the antisymmetric product of strongly-orthogonal geminals (APSG), the generalized valence bond-perfect pairing (GVB-PP), and the antisymmetrized geminal power (AGP) wavefunctions. The presented method employs wavefunctions of the same type as Richardson-Gaudin (RG) states, but which are not eigenvectors of a model Hamiltonian which would allow for more freedom in the mean-field. The general idea is to work with the same state in a primal picture in terms of pairs, and in a dual picture in terms of pair-holes. This leads to an asymmetric energy expression which may be optimized bivariationally, and is strictly variational when the two representations are consistent. The general approach may be useful in other contexts, such as for computationally feasible variational coupled-cluster methods.

physics.chem-ph↗
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↗
arXiv2022

Density Matrices of Seniority-Zero Geminal Wavefunctions

Scalar products and density matrix elements of closed-shell pair geminal wavefunctions are evaluated directly in terms of the pair amplitudes, resulting in an analogue of Wick's theorem for fermions or bosons. This expression is in general intractable, but it is shown how it becomes feasible in three distinct ways for Richardson-Gaudin (RG) states, the antisymmetrized geminal power, and the antisymmetrized product of strongly-orthogonal geminals. Dissociation curves for hydrogen chains are computed with off-shell RG states and the antisymmetrized product of interacting geminals. Both are near exact suggesting that the incorrect results observed with ground state RG states are fixable using a different RG state.

physics.chem-ph↗
arXiv2022

The temporal limits of predicting fault failure

Machine learning models using seismic emissions can predict instantaneous fault characteristics such as displacement in laboratory experiments and slow slip in Earth. Here, we address whether the acoustic emission (AE) from laboratory experiments contains information about near-future frictional behavior. The approach uses a convolutional encoder-decoder containing a transformer layer. We use as input progressively larger AE input time windows and progressively larger output friction time windows. The attention map from the transformer is used to interpret which regions of the AE contain hidden information corresponding to future frictional behavior. We find that very near-term predictive information is indeed contained in the AE signal, but farther into the future the predictions are progressively worse. Notably, information for predicting near future frictional failure and recovery are found to be contained in the AE signal. This first effort predicting future fault frictional behavior with machine learning will guide efforts for applications in Earth.

physics.geo-ph↗
arXiv2021

Perturbative corrections for Hartree-Fock-like Algebraic Bethe Ansatz analogue

Rayleigh Schrödinger perturbation theory corrections are developed for an algebraic Bethe ansatz of individual electrons. Numerical results are ambiguous and would need either an orbital optimization or a configuration interaction singles solution to be satisfactory. Two different expressions are computed to be certain that results are correct.

physics.chem-ph↗
arXiv2021

Predicting Fault Slip via Transfer Learning

Data-driven machine-learning for predicting instantaneous and future fault-slip in laboratory experiments has recently progressed markedly due to large training data sets. In Earth however, earthquake interevent times range from 10's-100's of years and geophysical data typically exist for only a portion of an earthquake cycle. Sparse data presents a serious challenge to training machine learning models. Here we describe a transfer learning approach using numerical simulations to train a convolutional encoder-decoder that predicts fault-slip behavior in laboratory experiments. The model learns a mapping between acoustic emission histories and fault-slip from numerical simulations, and generalizes to produce accurate results using laboratory data. Notably slip-predictions markedly improve using the simulation-data trained-model and training the latent space using a portion of a single laboratory earthquake-cycle. The transfer learning results elucidate the potential of using models trained on numerical simulations and fine-tuned with small geophysical data sets for potential applications to faults in Earth.

physics.geo-ph↗
arXiv2020

Autonomous Extraction of Millimeter-scale Deformation in InSAR Time Series Using Deep Learning

Systematic characterization of slip behaviours on active faults is key to unraveling the physics of tectonic faulting and the interplay between slow and fast earthquakes. Interferometric Synthetic Aperture Radar (InSAR), by enabling measurement of ground deformation at a global scale every few days, may hold the key to those interactions. However, atmospheric propagation delays often exceed ground deformation of interest despite state-of-the art processing, and thus InSAR analysis requires expert interpretation and a priori knowledge of fault systems, precluding global investigations of deformation dynamics. Here we show that a deep auto-encoder architecture tailored to untangle ground deformation from noise in InSAR time series autonomously extracts deformation signals, without prior knowledge of a fault's location or slip behaviour. Applied to InSAR data over the North Anatolian Fault, our method reaches 2 mm detection, revealing a slow earthquake twice as extensive as previously recognized. We further explore the generalization of our approach to inflation/deflation-induced deformation, applying the same methodology to the geothermal field of Coso, California.

physics.geo-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↗