Details
| Original language | English |
|---|---|
| Pages (from-to) | 5689-5703 |
| Number of pages | 15 |
| Journal | The Journal of Physical Chemistry A |
| Volume | 127 |
| Issue number | 27 |
| Early online date | 3 Jul 2023 |
| Publication status | Published - 13 Jul 2023 |
Abstract
Quantum-mechanical (QM) and classical embedding models approximate a supermolecular quantum-chemical calculation. This is particularly useful when the supermolecular calculation has a size that is out of reach for present QM models. Although QM and classical embedding methods share the same goal, they approach this goal from different starting points. In this study, we compare the polarizable embedding (PE) and frozen-density embedding (FDE) models. The former is a classical embedding model, whereas the latter is a density-based QM embedding model. Our comparison focuses on solvent effects on optical spectra of solutes. This is a typical scenario where super-system calculations including the solvent environment become prohibitively large. We formulate a common theoretical framework for PE and FDE models and systematically investigate how PE and FDE approximate solvent effects. Generally, differences are found to be small, except in cases where electron spill-out becomes problematic in the classical frameworks. In these cases, however, atomic pseudopotentials can reduce the electron-spill-out issue.
ASJC Scopus subject areas
- Chemistry(all)
- Physical and Theoretical Chemistry
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In: The Journal of Physical Chemistry A, Vol. 127, No. 27, 13.07.2023, p. 5689-5703.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Theoretical and Numerical Comparison of Quantum- and Classical Embedding Models for Optical Spectra
AU - Jansen, Marina
AU - Reinholdt, Peter
AU - Hedegård, Erik Donovan
AU - König, Carolin
N1 - This work has been supported by the Deutsche Forschungsgemeinschaft (DFG) through the Emmy Noether Young Group Leader Programme (project KO 5423/1-1). EDH thanks The Villum Foundation, Young Investigator Program (grant no. 29412), the Swedish Research Council (grant no. 2019-04205), and Independent Research Fund Denmark (grant no. 0252-00002B and grant no. 2064-00002B) for support. The computations were carried out on the cluster system at the Leibniz University Hannover, Germany, which is funded by the Leibniz University Hannover, the Lower Saxony Ministry of Science and Culture (MWK) and the DFG.
PY - 2023/7/13
Y1 - 2023/7/13
N2 - Quantum-mechanical (QM) and classical embedding models approximate a supermolecular quantum-chemical calculation. This is particularly useful when the supermolecular calculation has a size that is out of reach for present QM models. Although QM and classical embedding methods share the same goal, they approach this goal from different starting points. In this study, we compare the polarizable embedding (PE) and frozen-density embedding (FDE) models. The former is a classical embedding model, whereas the latter is a density-based QM embedding model. Our comparison focuses on solvent effects on optical spectra of solutes. This is a typical scenario where super-system calculations including the solvent environment become prohibitively large. We formulate a common theoretical framework for PE and FDE models and systematically investigate how PE and FDE approximate solvent effects. Generally, differences are found to be small, except in cases where electron spill-out becomes problematic in the classical frameworks. In these cases, however, atomic pseudopotentials can reduce the electron-spill-out issue.
AB - Quantum-mechanical (QM) and classical embedding models approximate a supermolecular quantum-chemical calculation. This is particularly useful when the supermolecular calculation has a size that is out of reach for present QM models. Although QM and classical embedding methods share the same goal, they approach this goal from different starting points. In this study, we compare the polarizable embedding (PE) and frozen-density embedding (FDE) models. The former is a classical embedding model, whereas the latter is a density-based QM embedding model. Our comparison focuses on solvent effects on optical spectra of solutes. This is a typical scenario where super-system calculations including the solvent environment become prohibitively large. We formulate a common theoretical framework for PE and FDE models and systematically investigate how PE and FDE approximate solvent effects. Generally, differences are found to be small, except in cases where electron spill-out becomes problematic in the classical frameworks. In these cases, however, atomic pseudopotentials can reduce the electron-spill-out issue.
UR - http://www.scopus.com/inward/record.url?scp=85164624706&partnerID=8YFLogxK
U2 - 10.48550/arXiv.2304.11682
DO - 10.48550/arXiv.2304.11682
M3 - Article
VL - 127
SP - 5689
EP - 5703
JO - The Journal of Physical Chemistry A
JF - The Journal of Physical Chemistry A
SN - 1089-5639
IS - 27
ER -