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Relativistic Quantum Chemistry of Heavy and Superheavy Elements: Fully Relativistic Coupled-Cluster Calculations for Molecules of Heavy and Transactinide Superheavy Elements

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Fundamental World of Quantum Chemistry

Abstract

It is well known that relativistic and electron correlation effects are very significant for atomic and molecular systems of heavy (Z ~ 80) and superheavy (Z ~ 100) elements. Relativistic effects in the electronic structure of atomic systems of these elements (upto Z ~120) were calculated in 1970’s; however, all-electron calculations of electron correlation effects for such atomic systems are nonexistent. The situation is much worse for molecular systems of the heavy and superheavy elements. Whereas all-electron fully relativistic molecular calculations have been recently reported for a few superheavy polyatomics, such as SgBr6 [G.L.Malli, J. Chem.Phys. 116, 5476 (2000)]; the all-electron correlation calculations for such polyatomics are too gargantuan even for the currently available supercomputing technology. We have discussed here our all-electron fully relativistic Dirac-Fock (Breit) calculations for a few representative molecular systems of these elements, In order to make the electron correlation calculations manageable for such systems, we report here the first relativistic coupled-cluster singles and doubles (RCCSD) along with the triples calculated via perturbation theory RCCSD(T) calculations correlating ~50-60 electrons for PbH4 and RfCl4. We have shown that both the relativistic and electron correlation effects are very significant and it is mandatory to include simultaneously both the effects calculated correctly and accurately for atomic and molecular systems of heavy and transactinide superheavy elements.

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Author information

Authors and Affiliations

  1. Department of Chemistry, Simon Fraser University, Burnaby, British Columbia, Canada, V5A 1S6

    Gulzari L. Malli

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  1. Gulzari L. Malli
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Editors and Affiliations

  1. Uppsala University, Uppsala, Sweden

    Erkki J. Brändas

  2. Bogoliubov Institute for Theoretical Physics, Kiev, Ukraine

    Eugene S. Kryachko

  3. University of Leuven, Leuven, Belgium

    Eugene S. Kryachko

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Malli, G.L. (2004). Relativistic Quantum Chemistry of Heavy and Superheavy Elements: Fully Relativistic Coupled-Cluster Calculations for Molecules of Heavy and Transactinide Superheavy Elements. In: Brändas, E.J., Kryachko, E.S. (eds) Fundamental World of Quantum Chemistry. Springer, Dordrecht. https://doi.org/10.1007/978-94-017-0448-9_16

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  • DOI: https://doi.org/10.1007/978-94-017-0448-9_16

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-90-481-6687-9

  • Online ISBN: 978-94-017-0448-9

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