1. Similarity transformation of the electronic Schrödinger equation via Jastrow factorization
- Author
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Werner Dobrautz, Ali Alavi, Kai Guther, David P. Tew, Hongjun Luo, Aron J. Cohen, Cohen, AJ [0000-0002-0873-2391], Dobrautz, W [0000-0001-6479-1874], Tew, DP [0000-0002-3220-4177], and Apollo - University of Cambridge Repository
- Subjects
General Physics and Astronomy ,010402 general chemistry ,01 natural sciences ,Schrödinger equation ,symbols.namesake ,Factorization ,5102 Atomic, Molecular and Optical Physics ,Physics - Chemical Physics ,Ionization ,0103 physical sciences ,Physical and Theoretical Chemistry ,Wave function ,Eigenvalues and eigenvectors ,Mathematical physics ,Physics ,Quantum Physics ,010304 chemical physics ,34 Chemical Sciences ,Matrix similarity ,0104 chemical sciences ,Condensed Matter - Other Condensed Matter ,Formalism (philosophy of mathematics) ,symbols ,3406 Physical Chemistry ,Hamiltonian (quantum mechanics) ,51 Physical Sciences - Abstract
By expressing the electronic wavefunction in an explicitly-correlated (Jastrow-factorised) form, a similarity-transformed effective Hamiltonian can be derived. The effective Hamiltonian is non-Hermitian and contains three-body interactions. The resulting ground-state eigenvalue problem can be solved projectively using a stochastic configuration-interaction formalism. Our approach permits use of highly flexible Jastrow functions, which we show to be effective in achieving extremely high accuracy, even with small basis sets. Results are presented for the total energies and ionisation potentials of the first-row atoms, achieving accuracy within a mH of the basis-set limit, using modest basis sets and computational effort., Comment: 6 pages, 1 figure
- Published
- 2019
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