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Potential energy surface discontinuities in local correlation methods.

Nicholas J Russ1, T Daniel Crawford

  • 1Department of Chemistry, Virginia Tech, Blacksburg, Virginia 24061, USA.

The Journal of Chemical Physics
|July 21, 2004
PubMed
Summary
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Local correlation methods do not show discontinuities in homolytic bond cleavage. However, heterolytic bond cleavage exhibits discontinuities, which can be significant for potential energy surfaces in computational chemistry.

Area of Science:

  • Computational Chemistry
  • Quantum Chemistry
  • Theoretical Chemistry

Background:

  • Local correlation methods are essential for accurate electronic structure calculations.
  • Pulay-Saebø orbital domain approach is a key technique in local correlation methods.
  • Potential energy surfaces (PES) describe molecular energy during reactions.

Purpose of the Study:

  • To investigate discontinuities in bond-breaking potential energy surfaces (PES) using local correlation methods.
  • To analyze the behavior of these discontinuities in different bond dissociation scenarios.
  • To understand the role of orbital localization in these phenomena.

Main Methods:

  • Utilized local correlation methods based on the Pulay-Saebø orbital domain approach.

Related Experiment Videos

  • Examined three prototypical dissociating systems: fluoromethane (C-F bond), singlet ketene (C-C bond), and propadienone (central C-C bond).
  • Employed the Pipek-Mezey orbital localization method.

    • Main Results:

    • No discontinuities were observed in homolytic bond cleavage due to limitations in separating charges with the Pipek-Mezey method.
    • Discontinuities were found in heterolytic bond cleavage for singlet ketene and propadienone, occurring at stretched and equilibrium geometries.
    • These discontinuities were generally small but comparable to localization errors in certain cases.

    Conclusions:

    • The Pipek-Mezey orbital localization method's inability to separate distant charges prevents discontinuities in homolytic bond breaking.
    • Heterolytic bond cleavage presents discontinuities in local correlation calculations, impacting PES accuracy.
    • Further research is needed to fully characterize and mitigate these discontinuities for reliable computational chemistry predictions.