Automated Selection of Active Orbital Spaces

Abstract

One of the key challenges of quantum-chemical multi-configuration methods is the necessity to manually select orbitals for the active space. This selection requires both expertise and experience and can therefore impose severe limitations on the applicability of this most general class of ab initio methods. A poor choice of the active orbital space may yield even qualitatively wrong results. This is obviously a severe problem, especially for wave function methods that are designed to be systematically improvable. Here, we show how the iterative nature of the density matrix renormalization group combined with its capability to include up to about one hundred orbitals in the active space can be exploited for a systematic assessment and selection of active orbitals. These benefits allow us to implement an automated approach for active orbital space selection, which can turn multi-configuration models into black box approaches.

arXiv comment29 pages, 10 figures, 5 tables

References in corpus (11)

• The density matrix renormalization group for ab initio quantum chemistry
• Tensor product methods and entanglement optimization for ab initio quantum chemistry
• Measuring orbital interaction using quantum information theory
• Controlling the accuracy of the density matrix renormalization group method: The Dynamical Block State Selection approach
• Quantum information analysis of electronic states at different molecular structures
• An Efficient Matrix Product Operator Representation of the Quantum-Chemical Hamiltonian
• Entanglement Measures for Single- and Multi-Reference Correlation Effects
• Two-site entropy and quantum phase transitions in low-dimensional models
• Density Matrix Renormalization Group with Efficient Dynamical Electron Correlation Through Range Separation
• DMRG-SCF study of the singlet, triplet, and quintet states of oxo-Mn(Salen)
• Determining Factors for the Accuracy of DMRG in Chemistry

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