Achieving High-Accuracy Intermolecular Interactions by Combining Coulomb-Attenuated Second-Order Møller-Plesset Perturbation Theory with Coupled Kohn-Sham Dispersion
| Autor: | Huang, Y, Goldey, M, Head-Gordon, M, Beran, GJO |
|---|---|
| Rok vydání: | 2014 |
| Předmět: | |
| Zdroj: | Journal of chemical theory and computation, vol 10, iss 5 Huang, Y; Goldey, M; Head-Gordon, M; & Beran, GJO. (2014). Achieving high-accuracy intermolecular interactions by combining Coulomb-attenuated second-order Møller-Plesset perturbation theory with coupled Kohn-Sham dispersion. Journal of Chemical Theory and Computation, 10(5), 2054-2063. doi: 10.1021/ct5002329. UC Berkeley: Retrieved from: http://www.escholarship.org/uc/item/6bn3z3zd |
| Popis: | The dispersion-corrected second-order Møller-Plesset perturbation theory (MP2C) approach accurately describes intermolecular interactions in many systems. MP2C, however, expends much computational effort to compute the long-range correlation with MP2, only to discard and replace those contributions with a simpler long-range dispersion correction based on intermolecular perturbation theory. Here, we demonstrate that one can avoid calculating the long-range MP2 correlation by attenuating the Coulomb operator, allowing the dispersion correction to handle the long-range interactions inexpensively. With relatively modest Coulomb attenuation, one obtains results that are very similar to those from conventional MP2C. With more aggressive attenuation, one can remove just enough short-range repulsive exchange-dispersion interactions to compensate for finite basis set errors. Doing so makes it possible to approach complete basis set limit quality results with only an aug-cc-pVTZ basis, resulting in substantial computational savings. Further computational savings could be achieved by reformulating the MP2C algorithm to exploit the increased sparsity of the two-electron integrals. © 2014 American Chemical Society. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|