Počet záznamů: 1
Reassessing Spin-Coupled (Full Generalized Valence Bond) Descriptions of Ozone Using Three-Center Bond Indices.
- 1.
SYSNO ASEP 0480523 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název Reassessing Spin-Coupled (Full Generalized Valence Bond) Descriptions of Ozone Using Three-Center Bond Indices. Tvůrce(i) Cooper, D.L. (GB)
Penotti, F.E. (IT)
Ponec, Robert (UCHP-M) RID, ORCID, SAIZdroj.dok. Computational and Theoretical Chemistry - ISSN 2210-271X
Roč. 1116, Sl (2017), s. 40-49Poč.str. 10 s. Jazyk dok. eng - angličtina Země vyd. NL - Nizozemsko Klíč. slova full GVB and spin-coupled ; PI-system in O3 ; domain-averaged fermi holes Vědní obor RIV CF - Fyzikální chemie a teoretická chemie Obor OECD Physical chemistry Institucionální podpora UCHP-M - RVO:67985858 UT WOS 000409152500004 EID SCOPUS 85008173487 DOI 10.1016/j.comptc.2016.12.010 Anotace 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. Pracoviště Ústav chemických procesů Kontakt Eva Jirsová, jirsova@icpf.cas.cz, Tel.: 220 390 227 Rok sběru 2018
Počet záznamů: 1