Accepted in ChemPhysChem. Two important points. First, as shown in the crystal cell figure below, the low-frequency study of the ephedrine molecular solid is one that is best considered in the context of two infinite chains (red and blue) that are strongly interacting along the chain and very weakly interacting between chains. The key point is the realization that the ephedrine molecular solid is not best considered as four molecules packed into a crystal cell. The original round of mode assignments, based only in crystal cell contents, was a very complicated list of relative motions and nearly irreconcilable collisions of in- and out-of-phase motions. Thinking outside-the-unit-cell and realizing that the mode motions could be described far more easily (and logically) as chains instead of packed molecules made the final assignment and analysis of the terahertz spectrum very straightforward. The lesson is to take a good look at your molecular solid before attempting to describe the motions and consider divide-and-conquer approaches if you see correlations.
The second reason I am specifically pleased with this paper is that it is the first real terahertz study using Crystal06 that employs multiple generalized gradient approximation density functionals (BP, PBE, PW91) and basis sets (6-31G(d,p) and 6-311G(d,p)) and shows that these multiple levels of theory provide very similar results. That has, generally, NOT been the case with the many previous DMol3 studies that required difference-dipole intensity calculations instead of the use of more rigorous Wannier function-based intensities possible within the Crystal06 code.
Patrick M. Hakey, Damian G. Allis, Matthew R. Hudson, Wayne Ouellette, and Timothy M. Korter
Department of Chemistry, 1-014 Center for Science and Technology, Syracuse University, Syracuse, NY 13244-4100, USA
Abstract: The terahertz (THz) spectrum of (1R,2S)-(-)-ephedrine from 8.0 to 100.0 cm-1 has been investigated at liquid-nitrogen (78.4 K) temperature. A complete structural analysis has been performed in conjunction with a vibrational assignment of the experimental spectrum using solid-state density functional theory (DFT). In order to obtain the crystallographic lattice constants at a temperature relevant for the DFT simulations, the compound has also been characterized by cryogenic single-crystal X-ray diffraction. Theoretical modeling (solid-state and isolated-molecule) of the compound includes the use of three generalized gradient approximation density functionals (BP, PBE, PW91) and two Gaussian-type basis sets (6-31G(d,p) and 6-311G(d,p)). Assignment of the THz spectrum is performed at a PW91/6-311G(d,p) level of theory, which provides the best solid-state simulation agreement with experiment. The solid-state analysis indicates that the seven experimental spectral features observed at liquid-nitrogen temperature are comprised of 13 IR-active vibrational modes. Of these modes, nine are external crystal vibrations and provide approximately 57% of the predicted spectral intensity.
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