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Zwitterionic structures of strained cis-pyramidalised disilenes – Fact or artifact

Glasovac, Zoran; Antol, Ivana; Vazdar, Mario; Margetić, Davor
Zwitterionic structures of strained cis-pyramidalised disilenes – Fact or artifact // Theoretical chemistry accounts, 124 (2009), 5-6; 421-430 doi:10.1007/s00214-009-0633-x (međunarodna recenzija, članak, znanstveni)

Zwitterionic structures of strained cis-pyramidalised disilenes – Fact or artifact

Glasovac, Zoran ; Antol, Ivana ; Vazdar, Mario ; Margetić, Davor

Theoretical chemistry accounts (1432-881X) 124 (2009), 5-6; 421-430

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
Quantum chemical calculations ; disilenes ; pyramidalization ; diradical character ; ring strain

A series of cis-pyramidalized disilenes was modeled by ab initio and DFT methods with the special emphasis on character of the wavefunction. Spin restricted DFT (RDFT) and MP2 approaches predicted qualitatively different structures of disilenes as the minima (deformed zwitterionic and symmetrical diradicaloid, respectively). Additional CASSCF and broken symmetry spin unrestricted DFT (BS-UDFT) calculations confirmed symmetrical structures as more reliable minimum. The only exception is highly strained 1, 4-disilabicyclo[2.2.0]hex-1, 4-ene where deformed zwitterionic structure is corroborated by most of the applied methods including high-level MR-AQCC calculation. Analysis of the wavefunction obtained for both deformed and symmetrical minima indicates a strong tendency of the RDFT method to prefer structures possessing a closed shell wavefunction even though a strong electron density shift occurs. The results obtained at CASSCF level of theory showed that for a correct description of geometries of such systems, a two-configurational wavefunction is needed at least. The BS-UDFT and spin restricted MP2 methods describe such “ diradicaloid” geometries of cis-pyramidalized disilenes qualitatively correct although from different reasons.

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Projekt / tema
098-0982933-2920 - Organski i bioorganski procesi u osnovnom i elektronski pobuđenim stanjima (Mirjana Maksić, )
098-0982933-3218 - 'Host-guest' međudjelovanja u policikličkim sustavima (Davor Margetić, )

Institut "Ruđer Bošković", Zagreb

Časopis indeksira:

  • Current Contents Connect (CCC)
  • Web of Science Core Collection (WoSCC)
    • Science Citation Index Expanded (SCI-EXP)
    • SCI-EXP, SSCI i/ili A&HCI
  • Scopus