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Second-Order Self-Consistent-Field Density-Matrix Renormalization Group

Chemical Physics 2017-08-14 v2 Strongly Correlated Electrons Computational Physics Quantum Physics

Abstract

We present a matrix-product state (MPS)-based quadratically convergent density-matrix renormalization group self-consistent-field (DMRG-SCF) approach. Following a proposal by Werner and Knowles (JCP 82, 5053, (1985)), our DMRG-SCF algorithm is based on a direct minimization of an energy expression which is correct to second-order with respect to changes in the molecular orbital basis. We exploit a simultaneous optimization of the MPS wave function and molecular orbitals in order to achieve quadratic convergence. In contrast to previously reported (augmented Hessian) Newton-Raphson and super-configuration-interaction algorithms for DMRG-SCF, energy convergence beyond a quadratic scaling is possible in our ansatz. Discarding the set of redundant active-active orbital rotations, the DMRG-SCF energy converges typically within two to four cycles of the self-consistent procedure

Keywords

Cite

@article{arxiv.1611.05972,
  title  = {Second-Order Self-Consistent-Field Density-Matrix Renormalization Group},
  author = {Yingjin Ma and Stefan Knecht and Sebastian Keller and Markus Reiher},
  journal= {arXiv preprint arXiv:1611.05972},
  year   = {2017}
}

Comments

40 pages, 5 figures, 3 tables