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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