A-VCI: A flexible method to efficiently compute vibrational spectra

Marc Odunlami (1) , Vincent Le Bris (1) , Didier Bégué (1) , Isabelle Baraille (1) , Olivier Coulaud (2)

1 IPREM - Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux
2 HiePACS - High-End Parallel Algorithms for Challenging Numerical Simulations

The adaptive vibrational configuration interaction algorithm has been introduced as a new method to efficiently reduce the dimension of the set of basis functions used in a vibrational configuration interaction process. It is based on the construction of nested bases for the discretization of the Hamiltonian operator according to a theoretical criterion that ensures the convergence of the method. In the present work, the Hamiltonian is written as a sum of products of operators. The purpose of this paper is to study the properties and outline the performance details of the main steps of the algorithm. New parameters have been incorporated to increase flexibility, and their influence has been thoroughly investigated. The robustness and reliability of the method are demonstrated for the computation of the vibrational spectrum up to 3000 cm−1 of a widely studied 6-atom molecule (acetonitrile). Our results are compared to the most accurate up to date computation; we also give a new reference calculation for future work on this system. The algorithm has also been applied to a more challenging 7-atom molecule (ethylene oxide). The computed spectrum up to 3200 cm−1 is the most accurate computation that exists today on such systems.

Domaines: Calcul parallèle, distribué et partagé [cs.DC]

Marc Odunlami, Vincent Le Bris, Didier Bégué, Isabelle Baraille, Olivier Coulaud. A-VCI: A flexible method to efficiently compute vibrational spectra. Journal of Chemical Physics, 2017, 146 (21), ⟨10.1063/1.4984266⟩. ⟨hal-01534134⟩