Enantiomeric Transitions in the Chiral Cluster Au₁₅Studied by a Reaction Coordinate Deduced from Molecular Dynamics Simulations

A recently developed modified basin hopping (MBH) optimization algorithm, combined with an energy function calculated by the semiempirical density functional tight-binding (DFTB) theory, was applied to determine the lowest-energy structures of Aun clusters with size n = 3-20. It was predicted from the DFTB/MBH optimization algorithm calculations that clusters Au10, Au15, and Au18 exhibit chiral properties; i.e., each of these three clusters possesses the same energy value and associated with it are two nonsuperposable mirror-image clusters. In the potential energy landscape, there thus exist multidimensional barriers separating the two enantiomers, and this lowest-energy double-well morphology is surrounded by potential-energy minima of higher energies. In this paper, we have chosen to study the chiral cluster Au15 by employing an isothermal Brownian-type molecular dynamics simulation to discern in greater detail its conformational transition from one enantiomer, say left, to its right counterpart. To facilitate our analysis of the simulation data, we transpose the multidimensional configurational space description to a lower dimensional collective variable (CV) space spanned by two geometry-relevant CVs. The thermally driven progression and mechanism of enantiomeric transitions between the left and right enantiomers will be our main focus, and the strategy is to dissect the time development of the CVs collected from different sets of independent simulation runs. From simulation data, we found that an understanding of the dynamics of enantiomeric transitions needs first to seek out the left and right enantiomers through a molecular modeling and visualizing program, then to ferret out and identify between the left and right enantiomers a symmetrical structure, and finally to define from the latter a reaction coordinate. We showed in this work that this single reaction coordinate is predictive in unraveling the left ⇌ right enantiomeric transition events, providing a specific inkling of the transition time span and its associated distribution which can be checked further for its reasonableness by the autocorrelation function and a vibrational analysis, all of which shed light on the mechanisms of transition.