Discontinuous changes in the electronic structure upon infinitesimal changes to the Hamiltonian are demonstrated. These are revealed in one and two electron molecular systems by full configuration interaction (FCI) calculations when the realm of the nuclear charge is extended to be fractional. FCI electron densities in these systems show dramatic changes in real space and illustrate the transfer, hopping, and removal of electrons. This is due to the particle nature of electrons seen in stretched systems and is a manifestation of an energy derivative discontinuity at constant number of electrons. Dramatic errors of density functional theory densities are seen in real space as this physics is missing from currently used approximations. The movements of electrons in these simple systems encapsulate those in real physical processes, from chemical reactions to electron transport and pose a great challenge for the development of new electronic structure methods.
Skip Nav Destination
Article navigation
28 January 2014
Research Article|
January 28 2014
Dramatic changes in electronic structure revealed by fractionally charged nuclei
Aron J. Cohen;
Aron J. Cohen
1Department of Chemistry, Lensfield Rd.,
University of Cambridge
, Cambridge CB2 1EW, United Kingdom
Search for other works by this author on:
Paula Mori-Sánchez
Paula Mori-Sánchez
a)
2Departamento de Química,
Universidad Autónoma de Madrid
, 28049 Madrid, Spain
Search for other works by this author on:
a)
Electronic mail: paula.mori@uam.es
J. Chem. Phys. 140, 044110 (2014)
Article history
Received:
August 09 2013
Accepted:
December 13 2013
Citation
Aron J. Cohen, Paula Mori-Sánchez; Dramatic changes in electronic structure revealed by fractionally charged nuclei. J. Chem. Phys. 28 January 2014; 140 (4): 044110. https://doi.org/10.1063/1.4858461
Download citation file:
Sign in
Don't already have an account? Register
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Sign in via your Institution
Sign in via your InstitutionPay-Per-View Access
$40.00