QTAIM and stress tensor interpretation of the (H2 O)5 potential energy surface

Tianlv Xu; James Farrell; Yuning Xu; Roya Momen; Steven R Kirk; Samantha Jenkins; David J Wales

doi:10.1002/jcc.24498

QTAIM and stress tensor interpretation of the (H₂ O)₅ potential energy surface

J Comput Chem. 2016 Dec 5;37(31):2712-2721. doi: 10.1002/jcc.24498. Epub 2016 Oct 3.

Authors

Tianlv Xu¹, James Farrell², Yuning Xu¹, Roya Momen¹, Steven R Kirk³, Samantha Jenkins⁴, David J Wales²

Affiliations

¹ College of Chemistry & Chemical Engineering, Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research and Key Laboratory of Resource Fine-Processing and Advanced Materials of Hunan Province of MOE, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan, 410081, China.
² Department of Chemistry, Lensfield Road, Cambridge University, UK.
³ College of Chemistry & Chemical Engineering, Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research and Key Laboratory of Resource Fine-Processing and Advanced Materials of Hunan Province of MOE, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan, 410081, China. steven.kirk@cantab.net.
⁴ College of Chemistry & Chemical Engineering, Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research and Key Laboratory of Resource Fine-Processing and Advanced Materials of Hunan Province of MOE, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan, 410081, China. samanthajsuman@gmail.com.

PMID: 27696459
DOI: 10.1002/jcc.24498

Abstract

Using the quantum theory of atoms in molecules a near complete combined directed spanning quantum topology phase diagram (QTPD) was constructed from the nine (H₂ O)₅ reaction-pathways and five unique Poincaré-Hopf solutions that were found after an extensive search of the MP2 potential energy surface. Two new energy minima that were predicted from earlier work are found and include the first (H₂ O)₅ conformer with a 3-D_QT quantum topology. The stress tensor Poincaré-Hopf relation indicated a preference for 2-D_QT (H₂ O)₅ topologies as well as the presence of coupling between shared-shell OH BCPs to the hydrogen-bond BCPs that share an H NCP. The complexity of the near complete combined QTPD was explained in terms of the O…O bonding interactions that were found in six of the nine (H₂ O)₅ reaction-pathways and for all points of the combined QTPD. The stabilizing role of the O…O bonding interactions from the values of the total local energy density was explored. © 2016 Wiley Periodicals, Inc.

Keywords: Poincaré-Hopf; hydrogen-bond; quantum theory of atoms in molecules; quantum topology phase diagram; stress tensor.

Publication types

Research Support, Non-U.S. Gov't