Coupled translation-rotation eigenstates of H2 in C60 and C70 on the spectroscopically optimized interaction potential

Effects of cage anisotropy on the energy level structure and assignments

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

Research output: Contribution to journalArticle

Abstract

We have developed a quantitatively accurate pairwise additive five-dimensional (5D) potential energy surface (PES) for H2 in C 60 through fitting to the recently published infrared (IR) spectroscopic measurements of this system for H2 in the vibrationally excited ν=1 state. The PES is based on the three-site H2 -C pair potential introduced in this work, which in addition to the usual Lennard-Jones (LJ) interaction sites on each H atom of H2 has the third LJ interaction site located at the midpoint of the H-H bond. For the optimal values of the three adjustable parameters of the potential model, the fully coupled quantum 5D calculations on this additive PES reproduce the six translation-rotation (T-R) energy levels observed so far in the IR spectra of H2 @ C60 to within 0.6%. This is due in large part to the greatly improved description of the angular anisotropy of the H2 -fullerene interaction afforded by the three-site H2 -C pair potential. The same H2 -C pair potential spectroscopically optimized for H2 @ C60 was also used to construct the pairwise additive 5D PES of H2 (ν=1) in C70. This PES, because of the lower symmetry of C70 (D5h) relative to that of C60 (Ih), exhibits pronounced anisotropy with respect to the direction of the translational motion of H2 away from the cage center, unlike that of H2 in C60. As a result, the T-R energy level structure of H2 in C70 from the quantum 5D calculations on the optimized PES, the quantum numbers required for its assignment, and the degeneracy patterns which arise from the T-R coupling for translationally excited H2 are all qualitatively different from those determined previously for H2 @ C60 [M. Xu, J. Chem. Phys. 128, 011101 (2008).

Original languageEnglish (US)
Article number224306
JournalJournal of Chemical Physics
Volume130
Issue number22
DOIs
StatePublished - 2009

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Potential energy surfaces
Electron energy levels
eigenvectors
Anisotropy
energy levels
potential energy
anisotropy
interactions
Fullerenes
Infrared radiation
translational motion
quantum numbers
fullerenes
infrared spectra
Atoms
symmetry
atoms

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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Coupled translation-rotation eigenstates of H2 in C60 and C70 on the spectroscopically optimized interaction potential : Effects of cage anisotropy on the energy level structure and assignments. / Xu, Minzhong; Sebastianelli, Francesco; Gibbons, Brittney R.; Bacic, Zlatko; Lawler, Ronald; Turro, Nicholas J.

In: Journal of Chemical Physics, Vol. 130, No. 22, 224306, 2009.

Research output: Contribution to journalArticle

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abstract = "We have developed a quantitatively accurate pairwise additive five-dimensional (5D) potential energy surface (PES) for H2 in C 60 through fitting to the recently published infrared (IR) spectroscopic measurements of this system for H2 in the vibrationally excited ν=1 state. The PES is based on the three-site H2 -C pair potential introduced in this work, which in addition to the usual Lennard-Jones (LJ) interaction sites on each H atom of H2 has the third LJ interaction site located at the midpoint of the H-H bond. For the optimal values of the three adjustable parameters of the potential model, the fully coupled quantum 5D calculations on this additive PES reproduce the six translation-rotation (T-R) energy levels observed so far in the IR spectra of H2 @ C60 to within 0.6{\%}. This is due in large part to the greatly improved description of the angular anisotropy of the H2 -fullerene interaction afforded by the three-site H2 -C pair potential. The same H2 -C pair potential spectroscopically optimized for H2 @ C60 was also used to construct the pairwise additive 5D PES of H2 (ν=1) in C70. This PES, because of the lower symmetry of C70 (D5h) relative to that of C60 (Ih), exhibits pronounced anisotropy with respect to the direction of the translational motion of H2 away from the cage center, unlike that of H2 in C60. As a result, the T-R energy level structure of H2 in C70 from the quantum 5D calculations on the optimized PES, the quantum numbers required for its assignment, and the degeneracy patterns which arise from the T-R coupling for translationally excited H2 are all qualitatively different from those determined previously for H2 @ C60 [M. Xu, J. Chem. Phys. 128, 011101 (2008).",
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AB - We have developed a quantitatively accurate pairwise additive five-dimensional (5D) potential energy surface (PES) for H2 in C 60 through fitting to the recently published infrared (IR) spectroscopic measurements of this system for H2 in the vibrationally excited ν=1 state. The PES is based on the three-site H2 -C pair potential introduced in this work, which in addition to the usual Lennard-Jones (LJ) interaction sites on each H atom of H2 has the third LJ interaction site located at the midpoint of the H-H bond. For the optimal values of the three adjustable parameters of the potential model, the fully coupled quantum 5D calculations on this additive PES reproduce the six translation-rotation (T-R) energy levels observed so far in the IR spectra of H2 @ C60 to within 0.6%. This is due in large part to the greatly improved description of the angular anisotropy of the H2 -fullerene interaction afforded by the three-site H2 -C pair potential. The same H2 -C pair potential spectroscopically optimized for H2 @ C60 was also used to construct the pairwise additive 5D PES of H2 (ν=1) in C70. This PES, because of the lower symmetry of C70 (D5h) relative to that of C60 (Ih), exhibits pronounced anisotropy with respect to the direction of the translational motion of H2 away from the cage center, unlike that of H2 in C60. As a result, the T-R energy level structure of H2 in C70 from the quantum 5D calculations on the optimized PES, the quantum numbers required for its assignment, and the degeneracy patterns which arise from the T-R coupling for translationally excited H2 are all qualitatively different from those determined previously for H2 @ C60 [M. Xu, J. Chem. Phys. 128, 011101 (2008).

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