Localized orbitals are representations of electronic structure, which are easier to interpret than delocalized, canonical orbitals. While unitary transformations from canonical orbitals into localized orbitals have long been known, existing techniques maximize localization without regard to coupling between orbitals. Especially in conjugated π spaces, orbitals are collapsed by unitary localization procedures into nonintuitive, strongly interacting units. Over-localization decreases interpretability, results in large values of interorbital coupling, and gives unmeaningful diagonal Fock energies. Herein, we introduce orbitals of intermediate localization that span between canonical and fully localized orbitals. To within a specified error, these orbitals preserve the diagonal nature of the Fock matrix while still introducing significant locality. In systems composed of molecular fragments, π spaces can be localized into weakly coupled units. Importantly, as the weakly coupled orbitals separate, highly coupled orbitals maintain their expected structure. The resulting orbitals therefore correspond well to chemical intuition and maintain accurate orbital energies, making this procedure unique among existing orbital localization techniques. This article focuses on the formation and physical analysis of orbitals that smoothly connect the known fully delocalized and fully localized limits.
Skip Nav Destination
CHORUS
Article navigation
7 July 2015
Research Article|
July 02 2015
Orbitals with intermediate localization and low coupling: Spanning the gap between canonical and localized orbitals
Paul M. Zimmerman;
Paul M. Zimmerman
a)
1Department of Chemistry,
University of Michigan
, Ann Arbor, Michigan 48109, USA
Search for other works by this author on:
Andrew R. Molina
;
Andrew R. Molina
1Department of Chemistry,
University of Michigan
, Ann Arbor, Michigan 48109, USA
Search for other works by this author on:
Peter Smereka
Peter Smereka
2Department of Mathematics,
University of Michigan
, Ann Arbor, Michigan 48109, USA
Search for other works by this author on:
1Department of Chemistry,
University of Michigan
, Ann Arbor, Michigan 48109, USA
2Department of Mathematics,
University of Michigan
, Ann Arbor, Michigan 48109, USA
a)
Author to whom correspondence should be addressed. Electronic mail: [email protected]
J. Chem. Phys. 143, 014106 (2015)
Article history
Received:
May 05 2015
Accepted:
June 16 2015
Citation
Paul M. Zimmerman, Andrew R. Molina, Peter Smereka; Orbitals with intermediate localization and low coupling: Spanning the gap between canonical and localized orbitals. J. Chem. Phys. 7 July 2015; 143 (1): 014106. https://doi.org/10.1063/1.4923084
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Citing articles via
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
CREST—A program for the exploration of low-energy molecular chemical space
Philipp Pracht, Stefan Grimme, et al.
Related Content
Efficient and accurate treatment of weak pairs in local CCSD(T) calculations
J. Chem. Phys. (October 2013)
NMR shielding tensors for density fitted local second-order Møller-Plesset perturbation theory using gauge including atomic orbitals
J. Chem. Phys. (August 2012)
SASS: A symmetry adapted stochastic search algorithm exploiting site symmetry
J. Chem. Phys. (March 2007)