Abstract
The Resolution of Identity (RI) technique has been employed to speed up the use of hybrid exchange-correlation (xc) functionals at the TDDFT level using the Hybrid Diagonal Approximation. The RI has been implemented within the polTDDFT algorithm (a complex damped polarization method) in the AMS/ADF suite of programs. A speedup factor of 30 has been obtained with respect to a previous numerical implementation, albeit with the same level of accuracy. Comparison of TDDFT simulations with the experimental photoabsorption spectra of the cluster series Au8n+4(SR)4n+8(n = 3-6; R = C6H5) showed the excellent accuracy and efficiency of the method. Results were compared with those obtained via the more simplified and computationally cheaper TDDFT+TB and sTDDFT methods. The present method represents an accurate as well as computationally affordable approach to predict photoabsorption spectra of complex species, realizing an optimal compromise between accuracy and computational efficiency, and is suitable for applications to large metal clusters with sizes up to several hundreds of atoms.
| Original language | English |
|---|---|
| Pages (from-to) | 9244-9257 |
| Number of pages | 14 |
| Journal | Journal of Physical Chemistry A |
| Volume | 127 |
| Issue number | 44 |
| Early online date | 31 Oct 2023 |
| DOIs | |
| Publication status | Published - 9 Nov 2023 |
Bibliographical note
Funding Information:P.D.A. and M.S. are grateful to Erik van Lenthe and Stan van Gisbergen of SCM (Amsterdam) for fruitful discussions and technical assistance during the implementation within the AMS/ADF program. Computational support from the CINECA supercomputing center within the ISCRA program is gratefully acknowledged. The authors are grateful to the Stiftung Beneficentia for a generous grant employed to set up a computational server. Support from Trieste University within the FRA program is gratefully acknowledged. Financial support from ICSC – Centro Nazionale di Ricerca in High Performance Computing, Big Data and Quantum Computing, funded by European Union – NextGenerationEU is gratefully acknowledged. Networking within the COST Action CA21101 “Confined molecular systems: from a new generation of materials to the stars” (COSY) supported by COST (European Cooperation in Science and Technology) is gratefully acknowledged.
Funding Information:
P.D.A. and M.S. are grateful to Erik van Lenthe and Stan van Gisbergen of SCM (Amsterdam) for fruitful discussions and technical assistance during the implementation within the AMS/ADF program. Computational support from the CINECA supercomputing center within the ISCRA program is gratefully acknowledged. The authors are grateful to the Stiftung Beneficentia for a generous grant employed to set up a computational server. Support from Trieste University within the FRA program is gratefully acknowledged. Financial support from ICSC - Centro Nazionale di Ricerca in High Performance Computing, Big Data and Quantum Computing, funded by European Union - NextGenerationEU is gratefully acknowledged. Networking within the COST Action CA21101 “Confined molecular systems: from a new generation of materials to the stars” (COSY) supported by COST (European Cooperation in Science and Technology) is gratefully acknowledged.
Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society
Funding
P.D.A. and M.S. are grateful to Erik van Lenthe and Stan van Gisbergen of SCM (Amsterdam) for fruitful discussions and technical assistance during the implementation within the AMS/ADF program. Computational support from the CINECA supercomputing center within the ISCRA program is gratefully acknowledged. The authors are grateful to the Stiftung Beneficentia for a generous grant employed to set up a computational server. Support from Trieste University within the FRA program is gratefully acknowledged. Financial support from ICSC – Centro Nazionale di Ricerca in High Performance Computing, Big Data and Quantum Computing, funded by European Union – NextGenerationEU is gratefully acknowledged. Networking within the COST Action CA21101 “Confined molecular systems: from a new generation of materials to the stars” (COSY) supported by COST (European Cooperation in Science and Technology) is gratefully acknowledged. P.D.A. and M.S. are grateful to Erik van Lenthe and Stan van Gisbergen of SCM (Amsterdam) for fruitful discussions and technical assistance during the implementation within the AMS/ADF program. Computational support from the CINECA supercomputing center within the ISCRA program is gratefully acknowledged. The authors are grateful to the Stiftung Beneficentia for a generous grant employed to set up a computational server. Support from Trieste University within the FRA program is gratefully acknowledged. Financial support from ICSC - Centro Nazionale di Ricerca in High Performance Computing, Big Data and Quantum Computing, funded by European Union - NextGenerationEU is gratefully acknowledged. Networking within the COST Action CA21101 “Confined molecular systems: from a new generation of materials to the stars” (COSY) supported by COST (European Cooperation in Science and Technology) is gratefully acknowledged.