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Low-Order Scaling Quasiparticle Self-Consistent GW for Molecules.

ABSTRACT: Low-order scaling GW implementations for molecules are usually restricted to approximations with diagonal self-energy. Here, we present an all-electron implementation of quasiparticle self-consistent GW for molecular systems. We use an efficient algorithm for the evaluation of the self-energy in imaginary time, from which a static non-local exchange-correlation potential is calculated via analytical continuation. By using a direct inversion of iterative subspace method, fast and stable convergence is achieved for almost all molecules in the GW100 database. Exceptions are systems which are associated with a breakdown of the single quasiparticle picture in the valence region. The implementation is proven to be starting point independent and good agreement of QP energies with other codes is observed. We demonstrate the computational efficiency of the new implementation by calculating the quasiparticle spectrum of a DNA oligomer with 1,220 electrons using a basis of 6,300 atomic orbitals in less than 4 days on a single compute node with 16 cores. We use then our implementation to study the dependence of quasiparticle energies of DNA oligomers consisting of adenine-thymine pairs on the oligomer size. The first ionization potential in vacuum decreases by nearly 1 electron volt and the electron affinity increases by 0.4 eV going from the smallest to the largest considered oligomer. This shows that the DNA environment stabilizes the hole/electron resulting from photoexcitation/photoattachment. Upon inclusion of the aqueous environment via a polarizable continuum model, the differences between the ionization potentials reduce to 130 meV, demonstrating that the solvent effectively compensates for the stabilizing effect of the DNA environment. The electron affinities of the different oligomers are almost identical in the aqueous environment.

SUBMITTER: Forster A

PROVIDER: S-EPMC8446457 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:We derive a low-scaling G0W0 algorithm for molecules using pair atomic density fitting (PADF) and an imaginary time representation of the Green's function and describe its implementation in the Slater type orbital (STO)-based Amsterdam density functional (ADF) electronic structure code. We demonstrate the scalability of our algorithm on a series of water clusters with up to 432 atoms and 7776 basis functions and observe asymptotic quadratic scaling with realistic threshold qualities controlling distance effects and basis sets of triple-ζ (TZ) plus double polarization quality. Also owing to a very small prefactor, a G0W0 calculation for the largest of these clusters takes only 240 CPU hours with these settings. We assess the accuracy of our algorithm for HOMO and LUMO energies in the GW100 database. With errors of 0.24 eV for HOMO energies on the quadruple-ζ level, our implementation is less accurate than canonical all-electron implementations using the larger def2-QZVP GTO-type basis set. Apart from basis set errors, this is related to the well-known shortcomings of the GW space-time method using analytical continuation techniques as well as to numerical issues of the PADF approach of accurately representing diffuse atomic orbital (AO) products. We speculate that these difficulties might be overcome by using optimized auxiliary fit sets with more diffuse functions of higher angular momenta. Despite these shortcomings, for subsets of medium and large molecules from the GW5000 database, the error of our approach using basis sets of TZ and augmented double-ζ (DZ) quality is decreasing with system size. On the augmented DZ level, we reproduce canonical, complete basis set limit extrapolated reference values with an accuracy of 80 meV on average for a set of 20 large organic molecules. We anticipate our algorithm, in its current form, to be very useful in the study of single-particle properties of large organic systems such as chromophores and acceptor molecules.

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Low-Order Scaling Quasiparticle Self-Consistent GW for Molecules.

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