Automated Identification of Relevant Frontier Orbitals for Chemical Compounds and Processes

Authors

  • Christopher J. Stein ETH Zurich Laboratorium fur Physikalische Chemie Vladimir-Prelog-Weg 2, CH-8093 Zurich, Switzerland
  • Markus Reiher ETH Zurich Laboratorium fur Physikalische Chemie Vladimir-Prelog-Weg 2, CH-8093 Zurich, Switzerland. markus.reiher@phys.chem.ethz.ch

DOI:

https://doi.org/10.2533/chimia.2017.170

Keywords:

Chemical reactions, Orbital entanglement, Quantum chemistry, Strong correlation

Abstract

Quantum-chemical multi-configurational methods are required for a proper description of static electron correlation, a phenomenon inherent to the electronic structure of molecules with multiple (near-)degenerate frontier orbitals. Here, we review how a property of these frontier orbitals, namely the entanglement entropy is related to static electron correlation. A subset of orbitals, the so-called active orbital space is an essential ingredient for all multi-configurational methods. We proposed an automated selection of this active orbital space, that would otherwise be a tedious and error prone manual procedure, based on entanglement measures. Here, we extend this scheme to demonstrate its capability for the selection of consistent active spaces for several excited states and along reaction coordinates.

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Published

2017-04-26

How to Cite

[1]
C. J. Stein, M. Reiher, Chimia 2017, 71, 170, DOI: 10.2533/chimia.2017.170.