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Problèmes d'algèbre extérieure liés au calcul de fonctions d'ondes électroniques produits de géminales

Abstract : In quantum chemistry, the electronic wave functions can be viewed as multivectors, therefore all problems translate into mathematical language thanks to the exterior algebra.We first recall some results related to the exterior and the interior products of the exterior algebra of a Hilbert space, which prove useful for quantum chemistry. We follow by presenting a method to find the annihilator ideal of a multivector, corresponding in physics to the excluded space by the Pauli principle, and this technique will be used in a later chapter.In a second step, we provide a summary of the key notions of the quantum formalism of fermionic systems and their counterpart from the point of view of the exterior algebra. We also recall the main approximation methods based on wave functions in quantum chemistry. We then introduce generalized versions of the concepts of seniority number and ionicity. These generalized numbers count respectively the partially occupied and fully occupied shells for any partition of the orbital space into shells. The Hermitian operators whose eigenspaces correspond to wave functions of definite generalized seniority or ionicity values are built. The generalized seniority numbers afford to establish refined hierarchies of configuration interaction spaces within those of fixed ordinary seniority.In the third and main chapter, we present the way that has led us to propose a new geminal product wave function ansatz where the geminals are not strongly orthogonal but satisfy weaker geometrical constraints to lower the computational effort without sacrificing the indistinguishability of the electrons. Our geometrical constraints translate into simple equations involving the traces of products of geminal matrices. In the simplest non-trivial model, a set of solutions is given by block-diagonal matrices where each block is of size 2x2 and consists of a Pauli matrix or a diagonal matrix, multiplied by a complex parameter to be optimized. With this simplified ansatz for geminals, the number of terms in the calculation of the matrix elements of quantum observables, like the Hamiltonian of the Schrödinger electronic equation, is considerably reduced.Finally, in the last part, we explain the implementation of our geminal product model in the computer code “Tonto”, which is a program and library for quantum crystallography and quantum chemistry written in the “Foo” language. The validity of our code has been tested on the calculation of the electronic energy of hydrogen chains. Moreover, a proof of principle that our ansatz gives significantly more accurate results than the strongly orthogonal geminal method has been established.
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Thomas Perez. Problèmes d'algèbre extérieure liés au calcul de fonctions d'ondes électroniques produits de géminales. Algèbres quantiques [math.QA]. Université Côte d'Azur, 2020. Français. ⟨NNT : 2020COAZ4060⟩. ⟨tel-03184787⟩

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