Nanoplasmonics simulations at the basis set limit through completenessoptimized, local numerical basis sets
Abstract
We present an approach for generating local numerical basis sets of improving accuracy for firstprinciples nanoplasmonics simulations within timedependent density functional theory. The method is demonstrated for copper, silver, and gold nanoparticles that are of experimental interest but computationally demanding due to the semicore delectrons that affect their plasmonic response. The basis sets are constructed by augmenting numerical atomic orbital basis sets by truncated Gaussiantype orbitals generated by the completenessoptimization 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 exchangecorrelation functionals. This work promotes the use of the local basis set approach of controllable accuracy in firstprinciples nanoplasmonics simulations and beyond.
 Authors:
 COMP Centre of Excellence, Department of Applied Physics, Aalto University School of Science, P.O. Box 11100, FI00076 Aalto (Finland)
 (United States)
 (Finland)
 Publication Date:
 OSTI Identifier:
 22416210
 Resource Type:
 Journal Article
 Resource Relation:
 Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 9; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
 Country of Publication:
 United States
 Language:
 English
 Subject:
 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACCURACY; ATOMS; COMPUTERIZED SIMULATION; COPPER; DENSITY FUNCTIONAL METHOD; DIMERS; ELECTRONS; GOLD; NANOPARTICLES; OPTIMIZATION; PERFORMANCE; PLASMONS; SILVER; TIME DEPENDENCE
Citation Formats
Rossi, Tuomas P., Email: tuomas.rossi@alumni.aalto.fi, Sakko, Arto, Puska, Martti J., Lehtola, Susi, Email: susi.lehtola@alumni.helsinki.fi, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, Nieminen, Risto M., and Dean’s Office, Aalto University School of Science, P.O. Box 11000, FI00076 Aalto. Nanoplasmonics simulations at the basis set limit through completenessoptimized, local numerical basis sets. United States: N. p., 2015.
Web. doi:10.1063/1.4913739.
Rossi, Tuomas P., Email: tuomas.rossi@alumni.aalto.fi, Sakko, Arto, Puska, Martti J., Lehtola, Susi, Email: susi.lehtola@alumni.helsinki.fi, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, Nieminen, Risto M., & Dean’s Office, Aalto University School of Science, P.O. Box 11000, FI00076 Aalto. Nanoplasmonics simulations at the basis set limit through completenessoptimized, local numerical basis sets. United States. doi:10.1063/1.4913739.
Rossi, Tuomas P., Email: tuomas.rossi@alumni.aalto.fi, Sakko, Arto, Puska, Martti J., Lehtola, Susi, Email: susi.lehtola@alumni.helsinki.fi, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, Nieminen, Risto M., and Dean’s Office, Aalto University School of Science, P.O. Box 11000, FI00076 Aalto. 2015.
"Nanoplasmonics simulations at the basis set limit through completenessoptimized, local numerical basis sets". United States.
doi:10.1063/1.4913739.
@article{osti_22416210,
title = {Nanoplasmonics simulations at the basis set limit through completenessoptimized, local numerical basis sets},
author = {Rossi, Tuomas P., Email: tuomas.rossi@alumni.aalto.fi and Sakko, Arto and Puska, Martti J. and Lehtola, Susi, Email: susi.lehtola@alumni.helsinki.fi and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 and Nieminen, Risto M. and Dean’s Office, Aalto University School of Science, P.O. Box 11000, FI00076 Aalto},
abstractNote = {We present an approach for generating local numerical basis sets of improving accuracy for firstprinciples nanoplasmonics simulations within timedependent density functional theory. The method is demonstrated for copper, silver, and gold nanoparticles that are of experimental interest but computationally demanding due to the semicore delectrons that affect their plasmonic response. The basis sets are constructed by augmenting numerical atomic orbital basis sets by truncated Gaussiantype orbitals generated by the completenessoptimization 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 exchangecorrelation functionals. This work promotes the use of the local basis set approach of controllable accuracy in firstprinciples nanoplasmonics simulations and beyond.},
doi = {10.1063/1.4913739},
journal = {Journal of Chemical Physics},
number = 9,
volume = 142,
place = {United States},
year = 2015,
month = 3
}

Coupled cluster calculations with all single and double excitations (CCSD) converge exceedingly slowly with the size of the oneparticle basis set. We assess the performance of a number of approaches for obtaining CCSD correlation energies close to the complete basisset limit in conjunction with relatively small DZ and TZ basis sets. These include global and systemdependent extrapolations based on the A + B/L{sup α} twopoint extrapolation formula, and the wellknown additivity approach that uses an MP2based basissetcorrection term. We show that the basis set convergence rate can change dramatically between different systems(e.g.it is slower for molecules with polar bonds and/ormore »

Gaussian basis sets for use in correlated molecular calculations. V. Corevalence basis sets for boron through neon
The correlationconsistent polarized valence basis sets (ccpVXZ) for the atoms boron through neon have been extended to treat core and corevalence correlation effects. Basis functions were added to the existing ccpVXZ sets to form correlationconsistent polarized corevalence sets (ccpCVXZ) in the usual pattern: Double zeta added (1{ital s}1{ital p}), triple zeta added (2{ital s}2{ital p}1{ital d}), quadruple zeta added (3{ital s}3{ital p}2{ital d}1{ital f}), and quintuple zeta added (4{ital s}4{ital p}3{ital d}2{ital f}1{ital g}). The exponents of the core functions were determined by minimizing the {ital difference} between allelectron and valenceonly correlation energies obtained from HF+1+2 calculations on the groundmore » 
Gaussian basis sets for use in correlated molecular calculations. VIII: Standard and augmented sextuple zeta correlation consistent basis sets for aluminum through argon
Standard and augmented correlation consistent sextuple zeta (ccpV6Z and augccpV6Z) basis sets have been determined for the secondrow atoms aluminum through argon. Using these sets, dissociation energies and spectroscopic constants for the ground states of HCl, PN, and P{sub 2} have been calculated using several theoretical methods, including MoellerPlesset perturbation theory, coupled cluster theory, and multireference configuration interaction theory (MRCI). The augccpV6Z and ccpV6Z sets yield dissociation energies that are estimated to be within 0.10.2 kcal/mol of the complete basis set limit for HCl and within 11.5 kcal/mol for PN and P{sub 2}. The MRCI and CCSD(T) methods are foundmore » 
Optimized gaussian basis sets for use with relativistic effective (core) potentials: K, Ca, GaKr
correlationconsistent valence basis sets were developed for the thirdrow main block elements (K, Ca, GaKr) for use with relativistic effective core potentials. These basis sets are somewhat larger than doublezeta in size, with polarization functions, and are balanced for use in both HartreeFock and correlation calculations. Spinorbit splittings for atoms and molecules are calculated and compared to experiment. These calculations use the approximate spinorbit operator from the relativistic effective core potentials. The use of these results in the calculations of accurate thermochemical data is discussed. 59 refs. 
Relativistic and Nonrelativistic EnergyOptimized Polarized Triple Zeta Basis Sets for the 4p, 5p and 6p Elements.
Relativistic and nonrelativistic valence triplezeta basis sets have been optimized at the selfconsistentfield (SCF) level with a Gaussian nuclear charge distribution for the 4p, 5p and 6p elements. Two d and one f function were optimized to correlate the valence space, and two f and one g function were optimized to correlate the (n  1)d shell. In addition, diffuse s and p functions were optimized at the SCF level and diffuse d and f functions were optimized at the multireference configuration interaction level for the negative ion. These basis sets are equivalents of the correlationconsistent basis sets. Prescriptions aremore »