Pushing the limits in accurate vibrational structure calculations: anharmonic frequencies of lithium fluoride clusters (LiF)n, n = 2–10

Literature Information

Publication Date 2014-06-26
DOI 10.1039/C4CP02264E
Impact Factor 3.676
Authors

Dominik Oschetzki, Guntram Rauhut


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Abstract

The vibrational spectra of a series of small lithium fluoride clusters, i.e. (LiF)n, n = 2–10, were studied by vibrational configuration interaction (VCI) calculations relying on potential energy surfaces including three-mode coupling terms and being obtained from explicitly correlated local coupled cluster calculations. Due to the account for anharmonicity effects, the simulated spectra allow for a direct comparison with experimental data and may thus help to identify clusters in the experiments. Even structurally closely related clusters can clearly be distinguished by infrared spectroscopy. The largest system in this study required more than 1000 basis functions in the electronic structure calculations and more than 107 configurations in the vibrational structure calculations and became computationally feasible only due to a combination of different approximations and highly parallelized algorithms.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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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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