Program Synthesis of Sparse Algorithms for Wave Function and Energy Prediction in Grid-Based Quantum Simulations

• Published in: Journal of chemical theory and computation Vol. 18; no. 4; pp. 2462 - 2478
• Main Author: Habershon, Scott
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 12.04.2022
• Subjects: Algorithms; Approximation; Digital video recorders; Eigenvalues; Eigenvectors; Electronic structure; Mathematical analysis; Molecular structure; Numerical methods; Optimization; Potential energy; Representations; Schrodinger equation; Spectroscopy and Excited States; Synthesis; Wave functions; Wave propagation
• ISSN: 1549-9618; 1549-9626; 1549-9626
• DOI: 10.1021/acs.jctc.2c00035

We have recently shown how program synthesis (PS), or the concept of “self-writing code”, can generate novel algorithms that solve the vibrational Schrödinger equation, providing approximations to the allowed wave functions for bound, one-dimensional (1-D) potential energy surfaces (PESs). The resulting algorithms use a grid-based representation of the underlying wave function ψ­(x) and PES V(x), providing codes which represent approximations to standard discrete variable representation (DVR) methods. In this Article, we show how this inductive PS strategy can be improved and modified to enable prediction of both vibrational wave functions and energy eigenvalues of representative model PESs (both 1-D and multidimensional). We show that PS can generate algorithms that offer some improvements in energy eigenvalue accuracy over standard DVR schemes; however, we also demonstrate that PS can identify accurate numerical methods that exhibit desirable computational features, such as employing very sparse (tridiagonal) matrices. The resulting PS-generated algorithms are initially developed and tested for 1-D vibrational eigenproblems, before solution of multidimensional problems is demonstrated; we find that our new PS-generated algorithms can reduce calculation times for grid-based eigenvector computation by an order of magnitude or more. More generally, with further development and optimization, we anticipate that PS-generated algorithms based on effective Hamiltonian approximations, such as those proposed here, could be useful in direct simulations of quantum dynamics via wave function propagation and evaluation of molecular electronic structure.