Orbital entanglement and CASSCF analysis of the Ru-NO bond in a Ruthenium nitrosyl complex

Physical Chemistry Chemical Physics : PCCP
Leon FreitagLeticia González

Abstract

Complete active space self-consistent field (CASSCF) wavefunctions and an orbital entanglement analysis obtained from a density-matrix renormalisation group (DMRG) calculation are used to understand the electronic structure, and, in particular, the Ru-NO bond of a Ru nitrosyl complex. Based on the configurations and orbital occupation numbers obtained for the CASSCF wavefunction and on the orbital entropy measurements evaluated for the DMRG wavefunction, we unravel electron correlation effects in the Ru coordination sphere of the complex. It is shown that Ru-NO π bonds show static and dynamic correlation, while other Ru-ligand bonds feature predominantly dynamic correlation. The presence of static correlation requires the use of multiconfigurational methods to describe the Ru-NO bond. Subsequently, the CASSCF wavefunction is analysed in terms of configuration state functions based on localised orbitals. The analysis of the wavefunctions in the electronic singlet ground state and the first triplet state provides a picture of the Ru-NO moiety beyond the standard representation based on formal oxidation states. A distinct description of the Ru and NO fragments is advocated. The electron configuration of Ru is an equally weighted s...Continue Reading

References

Dec 28, 1992·Science·E Culotta, D E Koshland
Jun 15, 1986·Physical Review. B, Condensed Matter·J P Perdew
Oct 1, 1993·Physical Review. B, Condensed Matter·S R White
Nov 9, 1992·Physical Review Letters·S R White
Oct 28, 1996·Physical Review Letters·J P PerdewM Ernzerhof
Apr 11, 2002·Chemical Reviews·Peter C Ford, Ivan M Lorkovic
Apr 11, 2002·Chemical Reviews·Anthony R Butler, Ian L Megson
Apr 22, 2004·Journal of the American Chemical Society·Ricardo García SerresKarl Wieghardt
Jun 3, 2004·Clinical Cancer Research : an Official Journal of the American Association for Cancer Research·Jeany M Rademaker-LakhaiJan H M Schellens
Dec 8, 2004·Current Topics in Medicinal Chemistry·Enzo AlessioGianni Sava
Apr 12, 2006·Physical Review Letters·O Legeza, J Sólyom
Jul 13, 2006·The Journal of Physical Chemistry. a·Björn O RoosPer-Olof Widmark
Nov 15, 2006·The Journal of Chemical Physics·Francesco AquilanteHenrik Koch
Oct 16, 2007·The Journal of Physical Chemistry. B·Jeanet Conradie, Abhik Ghosh
Jul 16, 2008·The Journal of Chemical Physics·Francesco AquilanteHenrik Koch
Jul 24, 2008·The Journal of Chemical Physics·Francesco AquilanteThomas Bondo Pedersen
Aug 9, 2008·Science·Aron J CohenWeitao Yang
Oct 24, 2008·The Journal of Physical Chemistry. a·Mariusz Radoń, Kristine Pierloot
Apr 10, 2009·The Journal of Physical Chemistry. a·Julianna Oláh, Jeremy N Harvey
Jun 6, 2009·Journal of Computational Chemistry·Francesco AquilanteRoland Lindh
Jul 25, 2009·The Journal of Chemical Physics·Francesco AquilanteBjörn Olof Roos
Nov 20, 2009·Physical Chemistry Chemical Physics : PCCP·Christopher J Cramer, Donald G Truhlar
Oct 1, 2008·Coordination Chemistry Reviews·Michael J Rose, Pradip K Mascharak
Jan 12, 2011·Annual Review of Physical Chemistry·Garnet Kin-Lic Chan, Sandeep Sharma
Aug 3, 2011·The Journal of Chemical Physics·Dongxia MaLaura Gagliardi
Dec 20, 2011·Nitric Oxide : Biology and Chemistry·Elia TfouniDouglas Wagner Franco
Apr 3, 2012·The Journal of Chemical Physics·Sandeep Sharma, Garnet Kin-Lic Chan
May 15, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Giovanni Finoto CaramoriElia Tfouni
Jun 19, 2012·Journal of Chemical Theory and Computation·Katharina BoguslawskiMarkus Reiher
Jul 25, 2013·Nature Chemistry·Yuki KurashigeTakeshi Yanai
Apr 1, 2014·Physical Chemistry Chemical Physics : PCCP·Matthieu MottetMarkus Reiher
Apr 22, 2014·Inorganic Chemistry·Leon Freitag, Leticia González
May 2, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Karla Furtado AndrianiRenato Luis Tame Parreira
Jul 2, 2014·Chimia·Sebastian F Keller, Markus Reiher
Jul 6, 2014·The Journal of Chemical Physics·Sebastian WoutersDimitri Van Neck

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Citations

Aug 13, 2015·The Journal of Physical Chemistry Letters·Frédéric GendronJochen Autschbach
Jan 2, 2016·The Journal of Physical Chemistry Letters·Chad E HoyerDonald G Truhlar
May 15, 2015·Physical Chemistry Chemical Physics : PCCP·Paweł TecmerPaul W Ayers
Jun 3, 2016·The Journal of Chemical Physics·Michael RoemeltGarnet K-L Chan
Nov 1, 2016·Journal of Molecular Modeling·Juan Sanz GarcíaJean-Louis Heully
Jan 18, 2017·Journal of Chemical Theory and Computation·Leon FreitagMarkus Reiher
Apr 25, 2019·Angewandte Chemie·Georg Monsch, Peter Klüfers
Oct 12, 2019·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Chantal Daniel, Christophe Gourlaouen
Jun 10, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Francesco TalottaMartial Boggio-Pasqua
Feb 14, 2020·Angewandte Chemie·Sebastian Mai, Leticia González
Jun 4, 2019·The Journal of Chemical Physics·Jan BrandejsÖrs Legeza
May 24, 2017·Scientific Reports·Szilárd SzalayÖrs Legeza
Aug 7, 2021·Physical Chemistry Chemical Physics : PCCP·Abhishek Khedkar, Michael Roemelt
Jan 13, 2021·Journal of Chemical Theory and Computation·Lexin DingChristian Schilling
Jul 28, 2018·Journal of Chemical Theory and Computation·Zhen LuoHaibo Ma
Nov 15, 2017·Journal of Chemical Theory and Computation·Francesco TalottaMartial Boggio-Pasqua
Aug 9, 2017·Journal of Chemical Theory and Computation·Andrew J AtkinsLeticia González
Sep 2, 2021·JACS Au·J Patrick Zobel, Leticia González
Sep 9, 2021·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Leon FreitagLeticia González

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Software Mentioned

CASPT2
TURBOMOLE
MAQUIS
CASSCF
MOLCAS
DMRG

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