Reassessing Spin-Coupled (Full Generalized Valence Bond) Descriptions of Ozone Using Three-Center Bond Indices.

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F67985858%3A_____%2F17%3A00480523" target="_blank" >RIV/67985858:_____/17:00480523 - isvavai.cz</a>

Result on the web

<a href="http://dx.doi.org/10.1016/j.comptc.2016.12.010" target="_blank" >http://dx.doi.org/10.1016/j.comptc.2016.12.010</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.comptc.2016.12.010" target="_blank" >10.1016/j.comptc.2016.12.010</a>

Result language

angličtina

Original language name

Reassessing Spin-Coupled (Full Generalized Valence Bond) Descriptions of Ozone Using Three-Center Bond Indices.

Original language description

Domain-averaged Fermi hole analysis is carried out for the ground state of O3 at its equilibrium geometry using a complete-active-space self-consistent field CASSCF(18,14) wavefunction, based on a slightly expanded full-valence active space. This initial analysis is augmented with an examination of the corresponding localized natural orbitals (LNOs) and of the numerical values obtained with a new improved definition of three-center bond indices for correlated singlet systems. Much the same pattern of LNOs is observed when using instead a subsequent internally-contracted multiconfiguration-reference configuration interaction construction, which also provides very similar values for the three-center bond indices. This gives us confidence to use such bond indices, alongside relative energies and the electric dipole moment, to assess the relative merits of various combinations of spin-coupled (full generalized valence bond) components with ten active electrons: four π, four σ bonding and the two nonbonding σ electrons associated with the central O atom. These multi-component valence bond descriptions were generated either with or without subsequent orbital reoptimization. The description of the π system which emerges from all of our analysis conforms to a standard model of three-center four-electron π bonding that incorporates a nontrivial degree of (partial) diradical character. Whereas certain combinations of ten-electron spin-coupled components can faithfully reproduce such a picture, none of the individual rival components appears to have sufficient flexibility on its own.

Czech name

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Czech description

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Type

J_imp - 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

Project

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Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2017

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Computational and Theoretical Chemistry

ISSN

2210-271X

e-ISSN

—

Volume of the periodical

1116

Issue of the periodical within the volume

Sl

Country of publishing house

NL - THE KINGDOM OF THE NETHERLANDS

Number of pages

10

Pages from-to

40-49

UT code for WoS article

000409152500004

EID of the result in the Scopus database

2-s2.0-85008173487