Software for the frontiers of quantum chemistry: An overview of developments in the Q-Chem 5 package.

This article summarizes technical advances contained in the fifth major release of the Q-Chem quantum chemistry program package, covering developments since 2015. A comprehensive library of exchange-correlation functionals, along with a suite of correlated many-body methods, continues to be a hallmark of the Q-Chem software. The many-body methods include novel variants of both coupled-cluster and configuration-interaction approaches along with methods based on the algebraic diagrammatic construction and variational reduced density-matrix methods.

Analytical nuclear gradients for the range-separated many-body dispersion model of noncovalent interactions.

An accurate treatment of the long-range electron correlation energy, including van der Waals (vdW) or dispersion interactions, is essential for describing the structure, dynamics, and function of a wide variety of systems. Among the most accurate models for including dispersion into density functional theory (DFT) is the range-separated many-body dispersion (MBD) method [A. Ambrosetti , , 2014, , 18A508], in which the correlation energy is modeled at short-range by a semi-local density functional and at long-range by a model system of coupled quantum harmonic oscillators.

A correlated-polaron electronic propagator: open electronic dynamics beyond the Born-Oppenheimer approximation.

In this work, we develop an approach to treat correlated many-electron dynamics, dressed by the presence of a finite-temperature harmonic bath. Our theory combines a small polaron transformation with the second-order time-convolutionless master equation and includes both electronic and system-bath correlations on equal footing. Our theory is based on the ab initio Hamiltonian, and is thus well-defined apart from any phenomenological choice of basis states or electronic system-bath coupling model.

New generalization of supersymmetric quantum mechanics to arbitrary dimensionality or number of distinguishable particles.

We present here a new approach to generalize supersymmetric quantum mechanics to treat multiparticle and multidimensional systems. We do this by introducing a vector superpotential in an orthogonal hyperspace. In the case of N distinguishable particles in three dimensions this results in a vector superpotential with 3N orthogonal components.

Supersymmetric quantum mechanics, excited state energies and wave functions, and the Rayleigh-Ritz variational principle: a proof of principle study.

In addition to ground state wave functions and energies, excited states and their energies are also obtained in a standard Rayleigh-Ritz variational calculation. However, their accuracy is generally much lower. Using the super-symmetric (SUSY) form of quantum mechanics, we show that better accuracy and more rapid convergence can be obtained by taking advantage of calculations of the ground states of higher sector SUSY Hamiltonians, followed by application of the SUSY "charge operators".

The Heisenberg-Weyl algebra on the circle and a related quantum mechanical model for hindered rotation.

We discuss a periodic variant of the Heisenberg-Weyl algebra, associated with the group of translations and modulations on the circle. Our study of uncertainty minimizers leads to a periodic version of canonical coherent states. Unlike the canonical, Cartesian case, there are states for which the uncertainty product associated with the generators of the algebra vanishes.