Capturing the Dynamic Correlation for Arbitrary Spin-Symmetry CASSCF Reference with Adiabatic Connection Approaches: Insights into the Electronic Structure of the Tetramethyleneethane Diradical
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F19%3A00507765" target="_blank" >RIV/61388955:_____/19:00507765 - isvavai.cz</a>
Result on the web
<a href="http://hdl.handle.net/11104/0298933" target="_blank" >http://hdl.handle.net/11104/0298933</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.jpclett.9b01582" target="_blank" >10.1021/acs.jpclett.9b01582</a>
Alternative languages
Result language
angličtina
Original language name
Capturing the Dynamic Correlation for Arbitrary Spin-Symmetry CASSCF Reference with Adiabatic Connection Approaches: Insights into the Electronic Structure of the Tetramethyleneethane Diradical
Original language description
The recently proposed approach to multireference dynamic correlation energy based on the adiabatic connection (AC) is extended to an arbitrary spin symmetry of the reference state. We show that both the spin-free AC approach and its computationally inexpensive approximation, AC0, when combined with a complete active space wave function, constitute viable alternatives to the perturbation-based and density-functional-based multiconfiguration methods. In particular, the AC0 approach, thanks to its favorable scaling with the system size and the size of the active space, allows for treating larger systems than its perturbation-based counterparts while maintaining comparable accuracy. We show the method’s robustness on illustrative chemical systems, including the elusive tetramethyleneethane (TME) diradical, potential energy surfaces of which present a challenge to most computational approaches. For the latter system, AC0 outperforms other methods, staying in close agreement with the full configuration interaction quantum Monte Carlo benchmark. A careful analysis of the contributions to the correlation energy of TME’s lowest singlet and triplet states reveals the subtle interplay of the dynamic and static correlation as the key to understanding the shape of the diradical’s potential energy surfaces.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
—
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2019
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Journal of Physical Chemistry Letters
ISSN
1948-7185
e-ISSN
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Volume of the periodical
10
Issue of the periodical within the volume
16
Country of publishing house
US - UNITED STATES
Number of pages
7
Pages from-to
4668-4674
UT code for WoS article
000481568500026
EID of the result in the Scopus database
2-s2.0-85070891434