Abstract
A number of fundamental problems with the topological analysis of molecular electron densities using the atoms in molecules (AIM) theory developed by Bader and coworkers are highlighted. In particular, contrary to statements made in the literature, we show that the local zero flux condition used in the AIM theory to define an atom in a molecule does not follow from the Schwinger variation principle, nor does it define unambiguously the atomic domains. Serious limitations of the definition of an atom in AIM theory also arise due to vibrational effects. A general definition of the structure of a molecular isomer based on a generalisation of the Born-Oppenheimer potential energy surface allow these limitations to be overcome.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callMore From: Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta)
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
