Communication: Active-space decomposition for molecular dimers

Shane M. Parker, Tamar Seideman, Mark A Ratner, Toru Shiozaki

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

We have developed an active-space decomposition strategy for molecular dimers that allows for the efficient computation of the dimer's complete-active-space wavefunction while only constructing the monomers' active-space wavefunctions. Dimer states are formed from linear combinations of direct products of localized orthogonal monomer states and Hamiltonian matrix elements are computed directly without explicitly constructing the product space. This decomposition is potentially exact in the limit where a full set of monomer states is included. The adiabatic states are then found by diagonalizing the dimer Hamiltonian matrix. We demonstrate the convergence of our method to a complete-active-space calculation of the full dimer with two test cases: the benzene and naphthalene dimers.

Original languageEnglish
Article number021108
JournalJournal of Chemical Physics
Volume139
Issue number2
DOIs
Publication statusPublished - Jul 14 2013

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ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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