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Ab initio study of the singlet-triplet splitting in reduced polyoxometalates

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Abstract

A valence bond analysis of the wave function of doubly reduced polyoxometales is presented, using the M6O19 Lindqvist structure as test case. By a unitary transformation of the delocalised valence orbitals to localised metal centred orbitals, the multiconfigurational wave function is mapped onto a valence bond function with three different types of configurations: the two electrons are on the same site, on neighbouring sites, or on next-nearest neighbour sites. The inspection of the relative weights of these configurations for triplet and singlet state shows that the triplet-coupled electrons are confined to a smaller volume, and hence have a higher energy than the singlet-coupled electrons. This is in line with the experimental observation that the doubly reduced polyoxometalates show non-mangetic behaviour.

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Acknowledgments

Prof. Santiago Olivella has been a reference for various generations of Spanish quantum chemists for his scientific rigour and for generously sharing his broad knowledge. It has been a privilege to receive his advices and to collaborate with him. Financial support has been provided by the Spanish Ministry of Education and Science (Projects CTQ2005-06909-C02-01/BQU and CTQU2005-08459-C02-02/BQU), and the Generalitat de Catalunya (Project 2005SGR-00104). Our group belongs to the "Theoretical and Computational Chemistry Network (Xarxa d’R+D+I en Química Teòrica i Computacional, XRQTC) supported by the Generalitat de Catalunya.

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Authors and Affiliations

  1. Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Marcel lí Domingo s/n, 43007, Tarragona, Spain

    Coen de Graaf, Rosa Caballol, Susanna Romo & Josep M. Poblet

  2. Institució Catalana de Recerca i Estudis Avançats (ICREA), Passeig Lluis Companys 23, 08010, Barcelona, Spain

    Coen de Graaf

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  1. Coen de Graaf
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  2. Rosa Caballol
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  3. Susanna Romo
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  4. Josep M. Poblet
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Correspondence to Coen de Graaf.

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Dedicated to Professor Santiago Olivella on the occasion of his 65th birthday and published as part of the Olivella Festschrift Issue.

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de Graaf, C., Caballol, R., Romo, S. et al. Ab initio study of the singlet-triplet splitting in reduced polyoxometalates. Theor Chem Acc 123, 3–10 (2009). https://doi.org/10.1007/s00214-009-0553-9

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