Nanoplasmonics simulations at the basis set limit through completeness-optimized, local numerical basis sets.
We present an approach for generating local numerical basis sets of improving accuracy for first-principles nanoplasmonics simulations within time-dependent density functional theory. The method is demonstrated for copper, silver, and gold nanoparticles that are of experimental interest but computationally demanding due to the semi-core d-electrons that affect their plasmonic response. The basis sets are constructed by augmenting numerical atomic orbital basis sets by truncated Gaussian-type orbitals generated by the completeness-optimization scheme, which is applied to the photoabsorption spectra of homoatomic metal atom dimers. We obtain basis sets of improving accuracy up to the complete basis set limit and demonstrate that the performance of the basis sets transfers to simulations of larger nanoparticles and nanoalloys as well as to calculations with various exchange-correlation functionals. This work promotes the use of the local basis set approach of controllable accuracy in first-principles nanoplasmonics simulations and beyond.
COMP Centre of Excellence, Department of Applied Physics, Aalto University School of Science, P.O. Box 11100, FI-00076 Aalto, Finland.
Tuomas P
TP
Rossi
COMP Centre of Excellence, Department of Applied Physics, Aalto University School of Science, P.O. Box 11100, FI-00076 Aalto, Finland.
Susi
S
Lehtola
COMP Centre of Excellence, Department of Applied Physics, Aalto University School of Science, P.O. Box 11100, FI-00076 Aalto, Finland.
Arto
A
Sakko
COMP Centre of Excellence, Department of Applied Physics, Aalto University School of Science, P.O. Box 11100, FI-00076 Aalto, Finland.
Martti J
MJ
Puska
COMP Centre of Excellence, Department of Applied Physics, Aalto University School of Science, P.O. Box 11100, FI-00076 Aalto, Finland.
Risto M
RM
Nieminen
D003198:Computer Simulation; D003300:Copper / Q000737:chemistry; D006046:Gold / Q000737:chemistry; D053768:Metal Nanoparticles / Q000737:chemistry*; D008956:Models, Chemical; D036103:Nanotechnology; D012834:Silver / Q000737:chemistry
D012834:Silver; D006046:Gold; D003300:Copper