Extremely localized molecular orbitals: Theory and applications

Maurizio Sironi, Alessandro Genoni, Monica Civera, Stefano Pieraccini, Michela Ghitti

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Abstract

Orbitals that are extremely localized on molecular fragments represent a powerful tool for a number of purposes: to cite a few examples, they allow to reduce strongly the complexity of calculations on large systems and are easily transferable from one molecule to another, providing a suitable and efficient way to build up the electronic structure of large molecules. Recently, we have developed efficient algorithms to determine extremely localized molecular orbitals (ELMOs), which will be reviewed in this paper. As a rigorous localization is strictly connected to a reduction in the number of variational parameters, which reflects into an increased value of the associated energy with respect to the Hartree Fock value, we have developed a number of strategies to relax the wavefunction built up using transferred localized orbitals. The extreme localization has also been exploited in connection with the "Divide and Conquer" technique to determine the electron densities of large polypeptides assembled from orbitals computed on small model molecules. Moreover, we will discuss the recent application of the ELMOs in the framework of the hybrid QM/MM methods to describe the frontier region. We will also show that the ELMOs can be used to extract chemical interpretations from numerical results. A variety of applications will be presented.

Original languageEnglish
Pages (from-to)685-698
Number of pages14
JournalTheoretical Chemistry Accounts
Volume117
Issue number5-6
DOIs
Publication statusPublished - May 2007

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Keywords

  • Divide and Conquer
  • Extremely localized molecular orbitals
  • Hyperconjugation
  • Transferability
  • VB approaches

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Sironi, M., Genoni, A., Civera, M., Pieraccini, S., & Ghitti, M. (2007). Extremely localized molecular orbitals: Theory and applications. Theoretical Chemistry Accounts, 117(5-6), 685-698. https://doi.org/10.1007/s00214-006-0200-7