Accurate ab initio spin densities

Katharina Boguslawski, Konrad H. Marti, O. Legeza, Markus Reiher

Research output: Contribution to journalArticle

54 Citations (Scopus)

Abstract

We present an approach for the calculation of spin density distributions for molecules that require very large active spaces for a qualitatively correct description of their electronic structure. Our approach is based on the density-matrix renormalization group (DMRG) algorithm to calculate the spin density matrix elements as a basic quantity for the spatially resolved spin density distribution. The spin density matrix elements are directly determined from the second-quantized elementary operators optimized by the DMRG algorithm. As an analytic convergence criterion for the spin density distribution, we employ our recently developed sampling-reconstruction scheme [J. Chem. Phys.2011, 134, 224101] to build an accurate complete-active-space configuration-interaction (CASCI) wave function from the optimized matrix product states. The spin density matrix elements can then also be determined as an expectation value employing the reconstructed wave function expansion. Furthermore, the explicit reconstruction of a CASCI-type wave function provides insight into chemically interesting features of the molecule under study such as the distribution of α and β electrons in terms of Slater determinants, CI coefficients, and natural orbitals. The methodology is applied to an iron nitrosyl complex which we have identified as a challenging system for standard approaches [J. Chem. Theory Comput.2011, 7, 2740].

Original languageEnglish
Pages (from-to)1970-1982
Number of pages13
JournalJournal of Chemical Theory and Computation
Volume8
Issue number6
DOIs
Publication statusPublished - Jun 12 2012

Fingerprint

Wave functions
density distribution
wave functions
configuration interaction
Molecules
determinants
Electronic structure
Mathematical operators
molecules
sampling
methodology
Iron
Sampling
electronic structure
iron
operators
orbitals
expansion
Electrons
coefficients

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computer Science Applications

Cite this

Accurate ab initio spin densities. / Boguslawski, Katharina; Marti, Konrad H.; Legeza, O.; Reiher, Markus.

In: Journal of Chemical Theory and Computation, Vol. 8, No. 6, 12.06.2012, p. 1970-1982.

Research output: Contribution to journalArticle

Boguslawski, K, Marti, KH, Legeza, O & Reiher, M 2012, 'Accurate ab initio spin densities', Journal of Chemical Theory and Computation, vol. 8, no. 6, pp. 1970-1982. https://doi.org/10.1021/ct300211j
Boguslawski, Katharina ; Marti, Konrad H. ; Legeza, O. ; Reiher, Markus. / Accurate ab initio spin densities. In: Journal of Chemical Theory and Computation. 2012 ; Vol. 8, No. 6. pp. 1970-1982.
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