Representation of potential energy surfaces by discrete polynomials: proton transfer in malonaldehyde
Literature Information
C. Adamo, V. Barone
A new method for the expansion of potential energy surfaces has been developed exploiting the peculiar properties of Hahn polynomials, a class of orthogonal polynomials of a discrete variable which generalize 3j vector coupling coefficients of angular momentum algebra. The method has been tested for the Hénon–Heiles potential, a typical model for coupled oscillators, and applied to the representation of the potential energy surface of malonaldehyde, a prototype system for intramolecular proton transfer in polyatomic molecules. The representation is obtained by fitting the polynomial expansion to a set of points calculated by the density functional theory method on a hyperspherical effective three-center coordinate system, in view of perspective quantum dynamical calculations of the proton transfer process.
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.











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