Quasi-free methyl rotation in zeolitic imidazolate framework-8

Wei Zhou; Hui Wu; Terrence J Udovic; John J Rush; Taner Yildirim

doi:10.1021/jp807033m

Quasi-free methyl rotation in zeolitic imidazolate framework-8

J Phys Chem A. 2008 Dec 11;112(49):12602-6. doi: 10.1021/jp807033m.

Authors

Wei Zhou¹, Hui Wu, Terrence J Udovic, John J Rush, Taner Yildirim

Affiliation

¹ NIST Center for Neutron Research, National Institute of Standards and Technology, 100 Bureau Dr., MS 6102, Gaithersburg, Maryland 20899, USA. wzhou@nist.gov

PMID: 19007199
DOI: 10.1021/jp807033m

Abstract

Using neutron inelastic scattering and diffraction, we have studied the quantum methyl rotation in zeolitic imidazolate framework-8 (ZIF-8: Zn(MeIM)(2), MeIM = 2-methylimidazolate). The rotational potential for the CH(3) groups in ZIF-8 is shown to be primarily 3-fold in character. The ground-state tunneling transitions at 1.4 K of 334 +/- 1 mueV for CH(3) groups in hydrogenated ZIF-8 (H-ZIF-8) and 33 +/- 1 mueV for CD(3) groups in deuterated ZIF-8 (D-ZIF-8) indicate that the barrier to internal rotation is small compared to almost all methylated compounds in the solid state and that methyl-methyl coupling is negligible. A 2.7 +/- 0.1 meV scattering peak assigned to the ground-state to first-excited-state, hindered rotational transition for H-ZIF-8, combined with a approximately 3 meV activation energy for methyl-group 3-fold jump reorientation estimated by quasi-elastic neutron scattering, suggests a very low methyl rotational barrier of approximately 7 meV. Results are compared to the CH(3) rotational amplitude at 3.5 K derived from neutron diffraction data, which are also consistent with a small 3-fold barrier and a very low energy rotational oscillation.