The V30 Benchmark Set for Anharmonic Vibrational Frequencies of Molecular Dimers

TL;DR

This paper introduces the V30 benchmark set of 30 molecular dimers to evaluate vibrational frequency calculations, highlighting the effectiveness of VPT2 combined with hindered rotor models for anharmonic intermolecular vibrations.

Contribution

It provides a new benchmark dataset and demonstrates the accuracy of advanced vibrational models for complex intermolecular modes.

Findings

VPT2 with hindered rotors accurately predicts fundamental frequencies.

Benchmark data set V30 covers diverse intermolecular interactions.

Comparison with experimental data validates the models.

Abstract

Intermolecular vibrations are extremely challenging to describe but are the most crucial part for determining entropy and hence free energies, and enable for instance the distinction between different crystal-packing arrangements of the same molecule via THz spectroscopy. Herein, we introduce a benchmark data set - V30 - containing 30 small molecular dimers with intermolecular interactions ranging from exclusively van-der-Waals dispersion to systems with hydrogen bonds. All calculations are performed with the gold standard of Quantum Chemistry CCSD(T). We discuss vibrational frequencies obtained via different models starting with the harmonic approximation over independent Morse oscillators up to second-order vibrational perturbation theory (VPT2), which allows a proper anharmonic treatment including coupling of vibrational modes. However, large amplitude motions present in many low-frequency intermolecular modes are problematic for VPT2. In analogy to the often used treatment for internal rotations, we replace such problematic modes by a simple one-dimensional hindered rotor model. We compare selected dimers with available experimental data or high-level calculations of potential energy surfaces and show that VPT2 in combination with hindered rotors can yield a very good description of fundamental frequencies for the discussed subset of dimers involving small and semi-rigid molecules.