The complex electronic structure and unusual potential energy curve of the chromium dimer have fascinated scientists for decades, with agreement between theory and experiment so far elusive. Here, we present a new ab initio simulation of the potential energy curve and vibrational spectrum that significantly improves on all earlier estimates. Our data support a shift in earlier experimental assignments of a cluster of vibrational frequencies by one quantum number.

The semistochastic heat-bath configuration interaction method is a selected configuration interaction plus perturbation theory method that has provided near-full configuration interaction (FCI) levels of accuracy for many systems with both single- and multi-reference character. However, obtaining accurate energies in the complete basis-set limit is hindered by the slow convergence of the FCI energy with respect to basis size.

We discovered a programming error and an error in some of the input files, which led us to recommend a reweighting factor that gives a positive and far from optimal time-step error. The reweighting factor in Eq. (9) of the original paper1 should be replaced by Δw=eTeff(S(R))+S(R))/2 With the corrected program and this choice of reweighting factor, we find time-step errors (shown in Figs. 1.4, the updated arXiv version of the paper,1 and the supplementary material), which are similar to the corresponding figures in the paper. For small time steps, they are nearly identical.

We study several approaches to orbital optimization in selected configuration interaction (SCI) plus perturbation theory methods and test them on the ground and excited states of three molecules using the semistochastic heat-bath configuration interaction method. We discuss the ways in which the orbital optimization problem in SCI resembles and differs from that in complete active space self-consistent field.

We investigate the renormalized perturbative triples correction together with the externally corrected coupled-cluster singles and doubles (ecCCSD) method. We use the density matrix renormalization group (DMRG) and heat-bath CI (HCI) as external sources for the ecCCSD equations. The accuracy is assessed for the potential energy surfaces of H2O, N2, and F2. We find that the triples correction significantly improves upon ecCCSD, and we do not see any instability of the renormalized triples with respect to dissociation.

We present a version of the T-moves approach for treating nonlocal pseudopotentials in diffusion Monte Carlo, which has much smaller time-step errors than the existing T-moves approaches, while at the same time preserving desirable features such as the upper-bound property for the energy. In addition, we modify the reweighting factor of the projector used in diffusion Monte Carlo to reduce the time-step error. The latter is applicable not only to pseudopotential calculations but also to all-electron calculations. © 2021 Author(s).

We report on the findings of a blind challenge devoted to determining the frozen-core, full configuration interaction (FCI) ground-state energy of the benzene molecule in a standard correlation-consistent basis set of double-ζ quality. As a broad international endeavor, our suite of wave function-based correlation methods collectively represents a diverse view of the high-accuracy repertoire offered by modern electronic structure theory.

The recently developed semistochastic heat-bath configuration interaction (SHCI) method is a systematically improvable selected configuration interaction plus perturbation theory method capable of giving essentially exact energies for larger systems than is possible with other such methods. We compute SHCI atomization energies for 55 molecules that have been used as a test set in prior studies because their atomization energies are known from experiment.

We believe that a necessary first step in understanding the ground-state properties of the spin-12 kagome Heisenberg antiferromagnet is a better understanding of this model's very large number of low-energy singlet states. A description of the low-energy states that is both accurate and amenable for numerical work may ultimately prove to have greater value than knowing only what these properties are, in particular, when they turn on the delicate balance of many small energies.

A large collaboration carefully benchmarks 20 first-principles many-body electronic structure methods on a test set of seven transition metal atoms and their ions and monoxides. Good agreement is attained between three systematically converged methods, resulting in experiment-free reference values. These reference values are used to assess the accuracy of modern emerging and scalable approaches to the many-electron problem. The most accurate methods obtain energies indistinguishable from experimental results, with the agreement mainly limited by the experimental uncertainties.