6533b7d0fe1ef96bd125adf8
RESEARCH PRODUCT
Virtual Orbital Many-Body Expansions: A Possible Route towards the Full Configuration Interaction Limit
Jürgen GaussFilippo LippariniJanus J. Eriksensubject
Chemical Physics (physics.chem-ph)Physics010304 chemical physicsBasis (linear algebra)Embarrassingly parallelFOS: Physical sciences010402 general chemistry01 natural sciencesFull configuration interactionLinear subspace0104 chemical sciencesRange (mathematics)Atomic orbitalComputational chemistryPhysics - Chemical Physics0103 physical sciencesGeneral Materials ScienceLimit (mathematics)Statistical physicsPhysical and Theoretical ChemistryEnergy (signal processing)description
In the present letter, it is demonstrated how full configuration interaction (FCI) results in extended basis sets may be obtained to within sub-kJ/mol accuracy by decomposing the energy in terms of many-body expansions in the virtual orbitals of the molecular system at hand. This extension of the FCI application range lends itself to two unique features of the current approach, namely that the total energy calculation can be performed entirely within considerably reduced orbital subspaces and may be so by means of embarrassingly parallel programming. Facilitated by a rigorous and methodical screening protocol and further aided by expansion points different from the Hartree-Fock solution, all-electron numerical results are reported for H$_2$O in polarized core-valence basis sets ranging from double-$\zeta$ (10 $e$, 28 $o$) to quadruple-$\zeta$ (10 $e$, 144 $o$) quality.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2017-01-01 |