Rigorous results in electronic structure calculations

Electronic structure calculations, in particular the computation of the ground state energy, lead to challenging problems in optimization. These problems are of enormous importance in quantum chemistry for calculations of properties of solids and molecules. Minimization methods for computing the ground state energy can be developed by employing a variational approach, where the second-order reduced density matrix defines the variable. This concept leads to large-scale semidefinite programming problems that provide a lower bound for the ground state energy. Upper bounds of the ground state energy can be calculated for example with the Hartree-Fock method. However, Nakata, Nakatsuji, Ehara, Fukuda, Nakata, and Fujisawa observed, that due to numerical errors the semidefinite solver produced erroneous results with a lower bound significantly larger than the Hartree-Fock upper bound. Violations within one mhartree were observed. We present here a method for solving electronic structure problems where all numerical errors are taken into consideration. In particular this method provides rigorous error bounds without violations as mentioned above.

DDC Class

004: Informatik

540: Chemie

600: Technik

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Rigorous results in electronic structure calculations