Infrared spectroscopy of small-molecule endofullerenes

TL;DR

This study uses infrared spectroscopy to analyze the quantum dynamics of hydrogen molecules trapped inside C$_{60}$ fullerenes, revealing their translational and rotational behaviors and deriving a detailed potential energy surface.

Contribution

It provides a comprehensive analysis of hydrogen endofullerenes using infrared spectroscopy and develops a five-dimensional potential energy model for H$_2$@C$_{60}$.

Findings

Identification of translational and rotational modes as infrared side bands.

Derivation of potential, rotational, vibrational, and dipole parameters.

Prediction and comparison of H$_2$ energies in C$_{70}$ based on the model.

Abstract

Hydrogen is one of the few molecules which has been incarcerated in the molecular cage of C$_{60}$ and forms endohedral supramolecular complex H$_2$@C$_{60}$. In this confinement hydrogen acquires new properties. Its translational motion becomes quantized and is correlated with its rotations. We applied infrared spectroscopy to study the dynamics of hydrogen isotopologs H$_2$, D$_2$ and HD incarcerated in C$_{60}$. The translational and rotational modes appear as side bands to the hydrogen vibrational mode in the mid infrared part of the absorption spectrum. Because of the large mass difference of hydrogen and C$_{60}$ and the high symmetry of C$_{60}$ the problem is identical to a problem of a vibrating rotor moving in a three-dimensional spherical potential. The translational motion within the C$_{60}$ cavity breaks the inversion symmetry and induces optical activity of H$_2$. We derive potential, rotational, vibrational and dipole moment parameters from the analysis of the infrared absorption spectra. Our results were used to derive the parameters of a pairwise additive five-dimensional potential energy surface for H$_2$@C$_{60}$. The same parameters were used to predict H$_2$ energies inside C$_{70}$[Xu et al., J. Chem. Phys., {\bf 130}, 224306 (2009)]. We compare the predicted energies and the low temperature infrared absorption spectra of H$_2$@C$_{70}$.