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Effects of symmetry breaking on the translation-rotation eigenstates of H2, HF, and H2O inside the fullerene C60


Splittings of the translation-rotation (TR) eigenstates of the solid light-molecule endofullerenes M@C60 (M = H2, H2O, HF) attributed to the symmetry breaking have been observed in the infrared (IR) and inelastic neutron scattering spectra of these species in the past couple of years. In the recent paper [Felker et al., Phys. Chem. Chem. Phys., 2017, 19, 31274], we established that the electrostatic, quadrupolar interaction between the guest molecule M and the twelve nearest-neighbor C60 cages of the solid is the main source of the symmetry breaking. The splittings of the three-fold degenerate ground states of the endohedral ortho-H2, ortho-H2O and the j=1 level of HF calculated using this model were found to be in excellent agreement with the experimental results. Utilizing the same electrostatic model, this theoretical study investigates the effects of the symmetry breaking on the excited TR eigenstates of the three species, and how they manifest in their simulated low-temperature (5-6 K) near-IR (NIR) and far-IR (FIR) spectra. The TR eigenstates are calculated variationally for both the major P and minor H crystal orientations. For the H orientation, the calculated splittings of all the TR levels of these species are less than 0.1 cm-1. For the dominant P orientation, the splittings vary strongly depending on the character of the excitations involved. In all the species, the splittings of the higher rotationally excited levels are comparable in magnitude to those for the j=1 levels. For the levels corresponding to purely translational excitations, the calculated splittings are about an order of magnitude smaller than those of the purely rotational eigenstates. Based on the computed TR eigenstates, the low-temperature NIR (for M = H2) and FIR (for M = HF, H2O) spectra are simulated for both the P and H orientations, and also combined as their weighted sum (0.15H + 0.85P). The weighted-sum spectra computed for M = H2 and HF match quantitatively the corresponding measured spectra, while for M = H2O the weighted-sum FIR spectrum predicts features that can potentially be observed experimentally.

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Publication details

The article was received on 23 Apr 2018, accepted on 23 May 2018 and first published on 23 May 2018

Article type: Paper
DOI: 10.1039/C8FD00082D
Citation: Faraday Discuss., 2018, Accepted Manuscript
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    Effects of symmetry breaking on the translation-rotation eigenstates of H2, HF, and H2O inside the fullerene C60

    Z. Bacic, V. Vlcek, D. Neuhauser and P. M. Felker, Faraday Discuss., 2018, Accepted Manuscript , DOI: 10.1039/C8FD00082D

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