Header

UZH-Logo

Maintenance Infos

GW in the Gaussian and plane waves scheme with application to linear acenes


Wilhelm, Jan; Del Ben, Mauro; Hutter, Jürg (2016). GW in the Gaussian and plane waves scheme with application to linear acenes. Journal of Chemical Theory and Computation, 12(8):3623-3635.

Abstract

We present an implementation of G0W0 and eigenvalue-self-consistent GW (evGW) in the Gaussian and plane waves scheme for molecules. We calculate the correlation self-energy for imaginary frequencies employing the resolution of the identity. The correlation self-energy for real frequencies is then evaluated by analytic continuation. This technique allows an efficient parallel implementation and application to systems with several hundreds of atoms. Various benchmark calculations are presented. In particular, the convergence with respect to the most important numerical parameters is assessed for the benzene molecule. Comparisons with respect to other G0W0 implementations are reported for a set of molecules, while the performance of the method has been measured for water clusters containing up to 480 atoms in a cc-TZVP basis. Additionally, G0W0 has been applied for studying the influence of the ligands on the gap of small CdSe nanoparticles. evGW has been employed to calculate the HOMO–LUMO gaps of linear acenes, linear chains formed of connected benzene rings. Distinct differences between the closed and the open-shell (broken-symmetry) evGW HOMO–LUMO gaps for long acenes are found. In future experiments, a comparison of measured HOMO–LUMO gaps and our calculated evGW values may be helpful to determine the electronic ground state of long acenes.

Abstract

We present an implementation of G0W0 and eigenvalue-self-consistent GW (evGW) in the Gaussian and plane waves scheme for molecules. We calculate the correlation self-energy for imaginary frequencies employing the resolution of the identity. The correlation self-energy for real frequencies is then evaluated by analytic continuation. This technique allows an efficient parallel implementation and application to systems with several hundreds of atoms. Various benchmark calculations are presented. In particular, the convergence with respect to the most important numerical parameters is assessed for the benzene molecule. Comparisons with respect to other G0W0 implementations are reported for a set of molecules, while the performance of the method has been measured for water clusters containing up to 480 atoms in a cc-TZVP basis. Additionally, G0W0 has been applied for studying the influence of the ligands on the gap of small CdSe nanoparticles. evGW has been employed to calculate the HOMO–LUMO gaps of linear acenes, linear chains formed of connected benzene rings. Distinct differences between the closed and the open-shell (broken-symmetry) evGW HOMO–LUMO gaps for long acenes are found. In future experiments, a comparison of measured HOMO–LUMO gaps and our calculated evGW values may be helpful to determine the electronic ground state of long acenes.

Statistics

Citations

8 citations in Web of Science®
8 citations in Scopus®
Google Scholar™

Altmetrics

Downloads

9 downloads since deposited on 16 Dec 2016
9 downloads since 12 months
Detailed statistics

Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:2016
Deposited On:16 Dec 2016 10:06
Last Modified:27 Jun 2017 00:00
Publisher:American Chemical Society (ACS)
ISSN:1549-9618
Additional Information:This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Chemical Theory and Computation, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jctc.6b00380.
Publisher DOI:https://doi.org/10.1021/acs.jctc.6b00380
PubMed ID:27348184

Download

Download PDF  'GW in the Gaussian and plane waves scheme with application to linear acenes'.
Preview
Content: Accepted Version
Filetype: PDF
Size: 1MB
View at publisher