Reassessing Spin-Coupled (Full Generalized Valence Bond) Descriptions of Ozone Using Three-Center Bond Indices.
Identifikátory výsledku
Kód výsledku v 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>
Výsledek na webu
<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>
Alternativní jazyky
Jazyk výsledku
angličtina
Název v původním jazyce
Reassessing Spin-Coupled (Full Generalized Valence Bond) Descriptions of Ozone Using Three-Center Bond Indices.
Popis výsledku v původním jazyce
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.
Název v anglickém jazyce
Reassessing Spin-Coupled (Full Generalized Valence Bond) Descriptions of Ozone Using Three-Center Bond Indices.
Popis výsledku anglicky
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.
Klasifikace
Druh
J<sub>imp</sub> - Článek v periodiku v databázi Web of Science
CEP obor
—
OECD FORD obor
10403 - Physical chemistry
Návaznosti výsledku
Projekt
—
Návaznosti
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Ostatní
Rok uplatnění
2017
Kód důvěrnosti údajů
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Údaje specifické pro druh výsledku
Název periodika
Computational and Theoretical Chemistry
ISSN
2210-271X
e-ISSN
—
Svazek periodika
1116
Číslo periodika v rámci svazku
Sl
Stát vydavatele periodika
NL - Nizozemsko
Počet stran výsledku
10
Strana od-do
40-49
Kód UT WoS článku
000409152500004
EID výsledku v databázi Scopus
2-s2.0-85008173487