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Accurate variational electronic structure calculations with the density matrix renormalization group

(2014)
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(UGent) and (UGent)
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Abstract
During the past fifteen years, the density matrix renormalization group (DMRG) has become increasingly important for ab initio quantum chemistry. Its underlying wavefunction ansatz, the matrix product state (MPS), is a low­-rank decomposition of the full configuration interaction tensor. The virtual dimension of the MPS, the rank of the decomposition, controls the size of the corner of the many­-body Hilbert space that can be reached with the ansatz. This parameter can be systematically increased until numerical convergence is reached. Whereas the MPS ansatz can only capture exponentially decaying correlation functions in the thermodynamic limit, and will therefore only yield an efficient description for noncritical one-dimensional systems, it can still be used as a variational ansatz for finite­-size systems. Rather large virtual dimensions are then required. The two most important aspects to reduce the corresponding computational cost are a proper choice and ordering of the active space orbitals, and the exploitation of the symmetry group of the Hamiltonian. By taking care of both aspects, DMRG becomes an efficient replacement for exact diagonalization in quantum chemistry. For hydrogen chains, accurate longitudinal static hyperpolarizabilities were obtained in the thermodynamic limit. In addition, the low-lying states of the carbon dimer were accurately resolved. DMRG and Hartree-­Fock theory have an analogous structure. The former can be interpreted as a self­-consistent mean­-field theory in the DMRG lattice sites, and the latter in the particles. It is possible to build upon this analogy to introduce post-­DMRG methods. Based on an approximate MPS, these methods provide improved ansätze for the ground state, as well as for excitations. Exponentiation of the single­-particle excitations for a Slater determinant leads to the Thouless theorem for Hartree-­Fock theory, an explicit nonredundant parameterization of the entire manifold of Slater determinants. For an MPS with open boundary conditions, exponentiation of the single-site excitations leads to the Thouless theorem for DMRG, an explicit nonredundant parameterization of the entire manifold of MPS wavefunctions. This gives rise to the configuration interaction expansion for DMRG. The Hubbard-­Stratonovich transformation lies at the basis of auxiliary field quantum Monte Carlo for Slater determinants. An analogous transformation for spin-­lattice Hamiltonians allows to formulate a promising variant for matrix product states.

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MLA
Wouters, Sebastian. “Accurate Variational Electronic Structure Calculations with the Density Matrix Renormalization Group.” 2014 : n. pag. Print.
APA
Wouters, S. (2014). Accurate variational electronic structure calculations with the density matrix renormalization group. Ghent University. Faculty of Sciences, Ghent, Belgium.
Chicago author-date
Wouters, Sebastian. 2014. “Accurate Variational Electronic Structure Calculations with the Density Matrix Renormalization Group”. Ghent, Belgium: Ghent University. Faculty of Sciences.
Chicago author-date (all authors)
Wouters, Sebastian. 2014. “Accurate Variational Electronic Structure Calculations with the Density Matrix Renormalization Group”. Ghent, Belgium: Ghent University. Faculty of Sciences.
Vancouver
1.
Wouters S. Accurate variational electronic structure calculations with the density matrix renormalization group. [Ghent, Belgium]: Ghent University. Faculty of Sciences; 2014.
IEEE
[1]
S. Wouters, “Accurate variational electronic structure calculations with the density matrix renormalization group,” Ghent University. Faculty of Sciences, Ghent, Belgium, 2014.
@phdthesis{4377157,
  abstract     = {During the past fifteen years, the density matrix renormalization group (DMRG) has become increasingly important for ab initio quantum chemistry. Its underlying wavefunction ansatz, the matrix product state (MPS), is a low­-rank decomposition of the full configuration interaction tensor. The virtual dimension of the MPS, the rank of the decomposition, controls the size of the corner of the many­-body Hilbert space that can be reached with the ansatz. This parameter can be systematically increased until numerical convergence is reached.
Whereas the MPS ansatz can only capture exponentially decaying correlation functions in the thermodynamic limit, and will therefore only yield an efficient description for noncritical one-dimensional systems, it can still be used as a variational ansatz for finite­-size systems. Rather large virtual dimensions are then required. The two most important aspects to reduce the corresponding computational cost are a proper choice and ordering of the active space orbitals, and the exploitation of the symmetry group of the Hamiltonian. By taking care of both aspects, DMRG becomes an efficient replacement for exact diagonalization in quantum chemistry. For hydrogen chains, accurate longitudinal static hyperpolarizabilities were obtained in the thermodynamic limit. In addition, the low-lying states of the carbon dimer were accurately resolved.
DMRG and Hartree-­Fock theory have an analogous structure. The former can be interpreted as a self­-consistent mean­-field theory in the DMRG lattice sites, and the latter in the particles. It is possible to build upon this analogy to introduce post-­DMRG methods. Based on an approximate MPS, these methods provide improved ansätze for the ground state, as well as for excitations. Exponentiation of the single­-particle excitations for a Slater determinant leads to the Thouless theorem for Hartree-­Fock theory, an explicit nonredundant parameterization of the entire manifold of Slater determinants. For an MPS with open boundary conditions, exponentiation of the single-site excitations leads to the Thouless theorem for DMRG, an explicit nonredundant parameterization of the entire manifold of MPS wavefunctions. This gives rise to the configuration interaction expansion for DMRG. The Hubbard-­Stratonovich transformation lies at the basis of auxiliary field quantum Monte Carlo for Slater determinants. An analogous transformation for spin-­lattice Hamiltonians allows to formulate a promising variant for matrix product states.},
  author       = {Wouters, Sebastian},
  isbn         = {9789461971944},
  language     = {eng},
  pages        = {IX, 209},
  publisher    = {Ghent University. Faculty of Sciences},
  school       = {Ghent University},
  title        = {Accurate variational electronic structure calculations with the density matrix renormalization group},
  year         = {2014},
}