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Coupled cluster valence bond theory for open-shell systems with application to very long range strong correlation in a polycarbene dimer
| Content Provider | United States Department of Energy Office of Scientific and Technical Information (OSTI.GOV) |
|---|---|
| Author | Small, David W. Head-Gordon, Martin |
| Organization | Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States) |
| Abstract | Here, the Coupled Cluster Valence Bond (CCVB) method, previously presented for closed-shell (CS) systems, is extended to open-shell (OS) systems. The theoretical development is based on embedding the basic OS CCVB wavefunction in a fictitious singlet super-system. This approach reveals that the OS CCVB amplitude equations are quite similar to those of CS CCVB, and thus that OS CCVB requires the same level of computational effort as CS CCVB, which is an inexpensive method. We present qualitatively correct CCVB potential energy curves for all low-lying spin states of P2 and Mn2+. CCVB is successfully applied to the low-lying spin states of some model linear polycarbenes, systems that appear to be a hindrance to standard density functionals. We examine an octa-carbene dimer in a side-by-side orientation, which, in the monomer dissociation limit, exhibits maximal strong correlation over the length of the polycarbene. |
| Sponsorship | USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22) |
| Related Links | https://www.osti.gov/biblio/1477258 |
| File Format | |
| ISSN | 00219606 |
| DOI | 10.1063/1.4991797 |
| Journal | Journal of Chemical Physics |
| Volume Number | 147 |
| Issue Number | 2 |
| Language | English |
| Publisher | American Institute of Physics (AIP) |
| Publisher Date | 2017-07-14 |
| Publisher Department | Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States) |
| Publisher Place | United States |
| Access Restriction | Open |
| Subject Keyword | INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY |
| Content Type | Text |
| Resource Type | Article |
| Subject | Physics and Astronomy Medicine Physical and Theoretical Chemistry |
