Machine learning thermodynamic perturbation theory (MLPT) is a promising approach to compute finite temperature properties when the goal is to compare several different levels of ab initio theory and/or to apply highly expensive computational methods. Indeed, starting from a production molecular dynamics trajectory, this method can estimate properties at one or more target levels of theory from only a small number of additional fixed-geometry calculations, which are used to train a machine learning model. However, as MLPT is based on thermodynamic perturbation theory (TPT), inaccuracies might arise when the starting point trajectory samples a configurational space which has a small overlap with that of the target approximations of interest. By considering case studies of molecules adsorbed in zeolites and several different density functional theory approximations, in this work we assess the accuracy of MLPT for ensemble total energies and enthalpies of adsorption. It is shown that problematic cases can be detected even without knowing reference results and that even in these situations it is possible to recover target level results within chemical accuracy by applying a machine-learning-based Monte Carlo (MLMC) resampling. Finally, on the basis of the ideas developed in this work, we assess and confirm the accuracy of recently published MLPT-based enthalpies of adsorption at the random phase approximation level, whose high computational cost would completely hinder a direct molecular dynamics simulation.

The configuration interaction approach provides a conceptually simple and powerful approach to solve the Schrodinger equation for realistic molecules and materials but is characterized by an unfavorable scaling, which strongly limits its practical applicability. Effectively selecting only the configurations that actually contribute to the wave function is a fundamental step toward practical applications. We propose a machine learning approach that iteratively trains a generative model to preferentially generate the important configurations. By considering molecular applications it is shown that convergence to chemical accuracy can be achieved much more rapidly with respect to random sampling or the Monte Carlo configuration interaction method. This work paves the way to a broader use of generative models to solve the electronic structure problem.

We provide numerical evidence that the nonlinear searching algorithm introduced by Wong and Meyer, rephrased in terms of quantum walks with effective nonlinear phase, can be extended to the finite 2-dimensional grid, keeping the same computational advantage with respect to the classical algorithms. For this purpose, we have considered the free lattice Hamiltonian, with linear dispersion relation introduced by Childs and Ge The numerical simulations showed that the walker finds the marked vertex in O(N1/4log3/4N) steps, with probability O(1/logN), for an overall complexity of O(N1/4log5/4N), using amplitude amplification. We also proved that there exists an optimal choice of the walker parameters to avoid the time measurement precision affecting the complexity searching time of the algorithm.

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