Local pair natural orbitals for excited states

Benjamin Helmich, Christof Hättig

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

We explore how in response calculations for excitation energies with wavefunction based (e.g., cou- pled cluster) methods the number of double excitation amplitudes can be reduced by means of trun- cated pair natural orbital (PNO) expansions and localized occupied orbitals. Using the CIS(D) ap- proximation as a test model, we find that the number of double excitation amplitudes can be reduced dramatically with minor impact on the accuracy if the excited state wavefunction is expanded in state-specific PNOs generated from an approximate first-order guess wavefunction. As for ground states, the PNO truncation error can also for excitation energies be controlled by a single threshold related to generalized natural occupation numbers. The best performance is found with occupied or- bitals which are localized by the Pipek-Mezey localization. For a large test set of excited states we find with this localization that already a PNO threshold of 10−8–10−7, corresponding to an average of only 40–80 PNOs per pair, is sufficient to keep the PNO truncation error for vertical excitation energies below 0.01 eV. This is a significantly more rapid convergence with the number doubles amplitudes than in domain-based local response approaches. We demonstrate that the number of significant excited state PNOs scales asymptotically linearly with the system size in the worst case of completely delocalized excitations and sub-linearly whenever the chromophore does not increase with the system size. Moreover, we observe that the flexibility of state-specific PNOs to adapt to the character of an excitation allows for an almost unbiased treatment of local, delocalized and charge transfer excited states.
Original languageEnglish
Article number214106
Pages (from-to)1-11
Number of pages11
JournalJournal of Chemical Physics
Volume135
Issue number21
DOIs
Publication statusPublished - 6 Dec 2011
Externally publishedYes

Keywords

  • charge exchange
  • configuration interactions
  • coupled cluster calculations
  • excited states
  • ground states
  • PNO calculations
  • wave functions

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