Time-dependent N-electron valence perturbation theory with matrix product state reference wavefunctions for large active spaces and basis sets: Applications to the chromium dimer and all-trans polyenes

Abstract

In earlier work [J. Chem. Phys. 144, 064102 (2016)], we introduced a time-dependent formulation of the second-order N-electron valence perturbation theory (t-NEVPT2) which (i) had a lower computational scaling than the usual internally-contracted perturbation formulation, and (ii) yielded the fully uncontracted NEVPT2 energy. Here, we present a combination of t-NEVPT2 with a matrix product state (MPS) reference wavefunction (t-MPS-NEVPT2) that allows to compute uncontracted dynamic correlation energies for large active spaces and basis sets, using the time-dependent density matrix renormalization group (td-DMRG) algorithm. In addition, we report a low-scaling MPS-based implementation of strongly-contracted NEVPT2 (sc-MPS-NEVPT2) that avoids computation of the four-particle reduced density matrix. We use these new methods to compute the dissociation energy of the chromium dimer and to study the low-lying excited states in all-trans polyenes (C${}_4$H${}_6$ to C${}_{24}$H${}_{26}$), incorporating dynamic correlation for reference wavefunctions with up to 24 active electrons and orbitals.

References in corpus (12)

• Orbital Optimization in the Density Matrix Renormalization Group, with applications to polyenes and β-carotene
• Low-energy spectrum of iron-sulfur clusters directly from many-particle quantum mechanics
• The density matrix renormalization group for ab initio quantum chemistry
• A spin-adapted Density Matrix Renormalization Group algorithm for quantum chemistry
• A canonical transformation theory from extended normal ordering
• A driven similarity renormalization group approach to quantum many-body problems
• Multi-reference perturbation theory with Cholesky decomposition for the density matrix renormalization group
• Automatic code generation enables nuclear gradient computations for fully internally contracted multireference theory
• A flexible multi-reference perturbation theory by minimizing the Hylleraas functional with matrix product states
• DMRG-SCF study of the singlet, triplet, and quintet states of oxo-Mn(Salen)
• A time-dependent formulation of multi-reference perturbation theory
• An Auxiliary-Field Quantum Monte Carlo Study of the Chromium Dimer

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