H2, HD, and D2 inside C60

Coupled translation-rotation eigenstates of the endohedral molecules from quantum five-dimensional calculations

Minzhong Xu, Francesco Sebastianelli, Zlatko Bacic, Ronald Lawler, Nicholas J. Turro

Research output: Contribution to journalArticle

Abstract

We have performed rigorous quantum five-dimensional (5D) calculations of the translation-rotation (T-R) energy levels and wave functions of H2, HD, and D2 inside C60. This work is an extension of our earlier investigation of the quantum T-R dynamics of H2 @ C60 [M. Xu, J. Chem. Phys. 128, 011101 (2008)] and uses the same computational methodology. Two 5D intermolecular potential energy surfaces (PESs) were employed, differing considerably in their well depths and the degree of confinement of the hydrogen molecule. Our calculations revealed pronounced sensitivity of the endohedral T-R dynamics to the differences in the interaction potentials, and to the large variations in the masses and the rotational constants of H2, HD, and D2. The T-R levels vary significantly in their energies and ordering on the two PESs, as well as from one isotopomer to another. Nevertheless, they all display the same distinctive patterns of degeneracies, which can be qualitatively understood and assigned in terms the model which combines the isotropic three-dimensional harmonic oscillator, the rigid rotor, and the coupling between the orbital and the rotational angular momenta of H2 HD D2. The quantum number j associated with the rotation of H2, HD, and D2 was found to be a good quantum number for H2 and D2 on both PESs, while most of the T-R levels of HD exhibit strong mixing of two or more rotational basis functions with different j values.

Original languageEnglish (US)
Article number064313
JournalJournal of Chemical Physics
Volume129
Issue number6
DOIs
StatePublished - 2008

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eigenvectors
Potential energy surfaces
Molecules
molecules
potential energy
quantum numbers
Rigid rotors
rigid rotors
Angular momentum
Wave functions
harmonic oscillators
Electron energy levels
Hydrogen
angular momentum
energy levels
wave functions
methodology
orbitals
sensitivity
hydrogen

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

H2, HD, and D2 inside C60 : Coupled translation-rotation eigenstates of the endohedral molecules from quantum five-dimensional calculations. / Xu, Minzhong; Sebastianelli, Francesco; Bacic, Zlatko; Lawler, Ronald; Turro, Nicholas J.

In: Journal of Chemical Physics, Vol. 129, No. 6, 064313, 2008.

Research output: Contribution to journalArticle

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