Discovering the Elusive Global Minimum in a Ternary Chiral Cluster: Rotational Spectra of Propylene Oxide Trimer.

Abstract

The chirality controlled conformational landscape of the trimer of propylene oxide (PO), a prototypical chiral molecule, was investigated using rotational spectroscopy and a range of theoretical tools for conformational searches and for evaluating vibrational contributions to effective structures. Two sets of homochiral (PO)3 rotational transitions were assigned and the associated conformers identified with theoretical support. One set of heterochiral (PO)3 transitions was assigned, but no structures generated by one of the latest, advanced conformational search codes could account for them. With the aid of a Python program, the carbon atom backbone and then the heterochiral (PO)3 structure were generated using 13C isotopic data. Excellent agreement between theoretical and experimental rotational constants and relative dipole moment components of all three conformers was achieved, especially after applying vibrational corrections to the rotational constants.