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Zwitterionic structures of strained cis-pyramidalized disilenes: fact or artifact

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Abstract

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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Notes

  1. The disilene 2 was also optimized by B3LYP and MP2 approaches using 6-311+G(d,p) basis set. The optimization resulted with very similar structures to those obtained with 6-31G(d) basis set indicating very weak basis set effect on geometrical parameters.

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Acknowledgments

Financial support of this work by the Ministry of Science, Education and Sport of Croatia through projects Nos. 098-0982933-2920 and 098-0982933-3218 is greatly acknowledged. We would also like to thank the Computing Center of the University of Zagreb (SRCE) for allocation of computer time on the Isabella cluster.

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Authors and Affiliations

  1. Division of Organic Chemistry and Biochemistry, Rudjer Bošković Institute, POB 180, 10002, Zagreb, Croatia

    Zoran Glasovac, Ivana Antol, Mario Vazdar & Davor Margetić

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  1. Zoran Glasovac
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  2. Ivana Antol
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  4. Davor Margetić
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Correspondence to Zoran Glasovac.

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Glasovac, Z., Antol, I., Vazdar, M. et al. Zwitterionic structures of strained cis-pyramidalized disilenes: fact or artifact. Theor Chem Acc 124, 421–430 (2009). https://doi.org/10.1007/s00214-009-0633-x

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