### Abstract

A stochastic method is proposed that evaluates the second-order perturbation corrections to the Dyson self-energies of a molecule (i.e., quasiparticle energies or correlated ionization potentials and electron affinities) directly and not as small differences between two large, noisy quantities. With the aid of a Laplace transform, the usual sum-of-integral expressions of the second-order self-energy in many-body Greens function theory are rewritten into a sum of just four 13-dimensional integrals, 12-dimensional parts of which are evaluated by Monte Carlo integration. Efficient importance sampling is achieved with the Metropolis algorithm and a 12-dimensional weight function that is analytically integrable, is positive everywhere, and cancels all the singularities in the integrands exactly and analytically. The quasiparticle energies of small molecules have been reproduced within a few mE_{h} of the correct values with 10^{8} Monte Carlo steps. Linear-to-quadratic scaling of the size dependence of computational cost is demonstrated even for these small molecules.

Original language | English (US) |
---|---|

Article number | 164111 |

Journal | Journal of Chemical Physics |

Volume | 138 |

Issue number | 16 |

DOIs | |

State | Published - Apr 28 2013 |

### Fingerprint

### ASJC Scopus subject areas

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

### Cite this

*Journal of Chemical Physics*,

*138*(16), [164111]. https://doi.org/10.1063/1.4801862