Monte Carlo MP2-F12 for Noncovalent Interactions: The C60Dimer

Alexander E. Doran, David L. Qiu, So Hirata

Research output: Contribution to journalArticlepeer-review

Abstract

A scalable stochastic algorithm is presented that can evaluate explicitly correlated (F12) second-order many-body perturbation (MP2) energies of weak, noncovalent, intermolecular interactions. It first transforms the formulas of the MP2 and F12 energy differences into a short sum of high-dimensional integrals of Green's functions in real space and imaginary time. These integrals are then evaluated by the Monte Carlo method augmented by parallel execution, redundant-walker convergence acceleration, direct-sampling autocorrelation elimination, and control-variate error reduction. By sharing electron-pair walkers across the supermolecule and its subsystems spanned by the joint basis set, the statistical uncertainty is reduced by one to 2 orders of magnitude in the MP2 binding energy corrected for the basis-set incompleteness and superposition errors. The method predicts the MP2-F12/aug-cc-pVDZ binding energy of 19.1 ± 4.0 kcal mol-1 for the C60 dimer at the center distance of 9.748 Å.

Original languageEnglish (US)
Pages (from-to)7344-7351
Number of pages8
JournalJournal of Physical Chemistry A
Volume125
Issue number33
DOIs
StatePublished - Aug 26 2021

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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