Relativistic quantum chemistry involving heavy atoms

  • Matteo De Santis
  • Leonardo BelapassiEmail author
  • Francesco Tarantelli
  • Loriano Storchi
The Quantum World of Molecules


Quantum chemistry is nowadays a term referring to a wide set of theoretical frameworks and models mainly relying on non-relativistic quantum mechanics. While, in most cases, the picture of the molecular structure and of the chemical reality provided by non-relativistic quantum chemistry is appropriate, we live in a universe with a finite speed of light. While neglecting variation of mass and velocity in the interaction of electrons and atomic nuclei is often safe, this is no more the case when heavy atoms are involved. In the present paper, we will briefly review the most rigorous way to include relativity in the modeling of molecular systems, that is to use the full 4-component (4c) formalism derived from the Dirac equation. Specifically, we will review the implementation that has been carried out in an effective 4c code called BERTHA. A recently developed method to gain deep insights into chemical bond is also presented and discussed in the 4c Dirac–Kohn–Sham context, the so-called natural orbitals for chemical valence/charge-displacement analysis.


Four-component Relativistic DFT Chemical bond Heavy atoms Relativistic effects 



We thank MIUR and the University of Perugia for the financial support of the AMIS project through the program “Dipartimenti di Eccellenza”. LS thanks University of Chieti-Pescara for the financial support.


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© Accademia Nazionale dei Lincei 2018

Authors and Affiliations

  1. 1.Dipartimento di Chimica, Biologia e BiotecnologieUniversità degli Studi di PerugiaPerugiaItaly
  2. 2.Istituto di Scienze e Tecnologie Molecolari, Consiglio Nazionale delle Ricerche c/o Dipartimento di Chimica, Biologia e BiotecnologieUniversità degli Studi di PerugiaPerugiaItaly
  3. 3.Istituto di Scienze e Tecnologie Molecolari, Consiglio Nazionale delle Ricerche c/o Dipartimento di FarmaciaUniversità degli Studi ‘G. D’Annunzio’ChietiItaly

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