Ring-polymer instanton method for calculating tunneling splittings

Richardson, Jeremy O.; Althorpe, Stuart C.

Abstract

The semiclassical instanton expression for the tunneling splitting between two symmetric wells is rederived, starting from the ring-polymer representation of the quantum partition function. This leads to simpler mathematics by replacing functional determinants with matrix determinants. By exploiting the simple Hückel-like structure of the matrices, we derive an expression for the instanton tunneling splitting in terms of a minimum on the potential surface of a linear polymer. The latter is a section cut out of a ring polymer, consisting of an infinite number of beads, which describes a periodic orbit on the inverted potential surface. The approach is straightforward to generalize to multiple dimensions, and we demonstrate that it is computationally practical by carrying out instanton calculations of tunneling splittings in HO2 and malonaldehyde in full dimensionality.

Citation

Richardson, J. O., & Althorpe, S. C. (2011). Ring-polymer instanton method for calculating tunneling splittings. The Journal of Chemical Physics, 134(5), Article 054109. https://doi.org/10.1063/1.3530589

• Journal Article Type: Article
• Acceptance Date: Dec 3, 2010
• Online Publication Date: Feb 7, 2011
• Publication Date: Feb 7, 2011
• Deposit Date: Feb 7, 2016
• Publicly Available Date: Jun 26, 2018
• Journal: Journal of Chemical Physics
• Print ISSN: 0021-9606
• Electronic ISSN: 1089-7690
• Publisher: American Institute of Physics
• Peer Reviewed: Peer Reviewed
• Volume: 134
• Issue: 5
• Article Number: 054109
• DOI: https://doi.org/10.1063/1.3530589
• Public URL: https://durham-repository.worktribe.com/output/1420645