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Electronic g Tensors in U V Complexes–A Computational Study
Author(s) -
Moylan Helen M.,
McDouall Joseph J W.
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201701058
Subject(s) - computation , tensor (intrinsic definition) , electronic structure , complete active space , simple (philosophy) , field (mathematics) , interpretation (philosophy) , computer science , computational chemistry , state (computer science) , statistical physics , quantum chemical , chemistry , theoretical physics , physics , molecule , quantum mechanics , mathematics , algorithm , pure mathematics , molecular orbital , philosophy , epistemology , programming language
The theory and computation of EPR parameters from first principles has seen a great deal of development over the past two decades. In particular, various techniques for the computation of the electronic g tensor have been implemented in many quantum chemistry packages. These methods have been successfully applied to paramagnetic organic species and transition metal systems. The situation is less well‐understood and established in the case of actinide‐containing molecules and there is a dearth of experimental data available for validation of computations. In this study quantum chemical techniques have been used to evaluate the g tensor for U V complexes, for which experimental data are available for comparison. The g tensors were calculated using relatively simple, state‐averaged complete active space self‐consistent field (SA‐CASSCF) calculations. This approach is shown to be capable of providing useful accuracy. Aspects of the computations that should be refined to provide a more quantitative approach are discussed. The key features of the underlying electronic structure that influence the computed g values are delineated, providing a simple physical picture of these subtle molecular properties.