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采用TDDFT+U方法计算的含4至923个原子的银团簇和纳米颗粒的光谱。

Optical spectra of silver clusters and nanoparticles from 4 to 923 atoms from the TDDFT+U method.

作者信息

Chaudhary Mohit, Weissker Hans-Christian

机构信息

Aix-Marseille University, CNRS, CINaM UMR 7325, 13288, Marseille, France.

European Theoretical Spectroscopy Facility, .

出版信息

Nat Commun. 2024 Oct 25;15(1):9225. doi: 10.1038/s41467-024-53428-6.


DOI:10.1038/s41467-024-53428-6
PMID:39455587
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11511974/
Abstract

The localized surface-plasmon resonances of coinage-metal clusters and nanoparticles enable many applications, the conception and necessary optimization of which require precise theoretical description and understanding. However, for the size range from few-atom clusters through nanoparticles of a few nanometers, where quantum effects and atomistic structure play a significant role, none of the methods employed previously has been able to provide high-quality spectra for all sizes. The main problem is the description of the filled shells of d electrons which influence the optical response decisively. We show that the DFT+U method, employed with real-time time-dependent density-functional theory calculations (RT-TDDFT), provides spectra in good agreement with experiment for silver clusters ranging from 4 to 923 atoms, the latter representing a nanoparticle of 3 nm. Both the electron-hole-type discrete spectra of the smallest clusters and the broad plasmon resonances of the larger sizes are obtained. All calculations use the value of the effective U parameter that provides good results in bulk silver. The agreement with experiment for all sizes shows that the U parameter is surprisingly transferable. Our results open the pathway for calculations of many practically relevant systems including clusters coupled to bio-molecules or to other nano-objects.

摘要

硬币金属团簇和纳米颗粒的局域表面等离子体共振可实现多种应用,而这些应用的概念及必要的优化需要精确的理论描述和理解。然而,对于从几原子团簇到几纳米纳米颗粒的尺寸范围,其中量子效应和原子结构起着重要作用,以前使用的任何方法都无法为所有尺寸提供高质量的光谱。主要问题在于对影响光学响应的d电子满壳层的描述。我们表明,结合实时含时密度泛函理论计算(RT-TDDFT)使用的DFT+U方法,对于4至923个原子的银团簇(后者代表一个3nm的纳米颗粒)能给出与实验结果高度吻合的光谱。既能得到最小团簇的电子-空穴型离散光谱,也能得到较大尺寸团簇的宽等离子体共振。所有计算都使用了在块状银中能给出良好结果的有效U参数值。所有尺寸下与实验结果的吻合表明U参数具有惊人的可转移性。我们的结果为计算许多实际相关系统开辟了道路,包括与生物分子或其他纳米物体耦合的团簇。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b8d8/11511974/a01fd92b7ec5/41467_2024_53428_Fig5_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b8d8/11511974/03b212122ec8/41467_2024_53428_Fig1_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b8d8/11511974/a3dc825ae67c/41467_2024_53428_Fig2_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b8d8/11511974/5e2dbe4753a3/41467_2024_53428_Fig3_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b8d8/11511974/936cd94a1b03/41467_2024_53428_Fig4_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b8d8/11511974/a01fd92b7ec5/41467_2024_53428_Fig5_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b8d8/11511974/03b212122ec8/41467_2024_53428_Fig1_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b8d8/11511974/a3dc825ae67c/41467_2024_53428_Fig2_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b8d8/11511974/5e2dbe4753a3/41467_2024_53428_Fig3_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b8d8/11511974/936cd94a1b03/41467_2024_53428_Fig4_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b8d8/11511974/a01fd92b7ec5/41467_2024_53428_Fig5_HTML.jpg

相似文献

[1]
Optical spectra of silver clusters and nanoparticles from 4 to 923 atoms from the TDDFT+U method.

Nat Commun. 2024-10-25

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引用本文的文献

[1]
Development of Real-Time TDDFT Program with -Point Sampling and DFT + in a Gaussian and Plane Waves Framework.

J Chem Theory Comput. 2025-2-25

本文引用的文献

[1]
Accurate prediction of the optical properties of nanoalloys with both plasmonic and magnetic elements.

Nat Commun. 2024-1-27

[2]
Visualizing screening in noble-metal clusters: static dynamic.

Phys Chem Chem Phys. 2023-1-18

[3]
Metal cluster plasmons analyzed by energy-resolved photoemission.

Phys Chem Chem Phys. 2023-1-18

[4]
The Missing Link: Au(SPh-Bu) Janus Nanoparticle with Molecular and Bulk-Metal-like Properties.

J Am Chem Soc. 2020-9-16

[5]
Octopus, a computational framework for exploring light-driven phenomena and quantum dynamics in extended and finite systems.

J Chem Phys. 2020-3-31

[6]
Optical properties of size selected neutral Ag clusters: electronic shell structures and the surface plasmon resonance.

Nanoscale. 2018-11-15

[7]
Plasmonic Biosensing.

Chem Rev. 2018-9-24

[8]
Surface-Enhanced Raman Spectroscopy for Bioanalysis: Reliability and Challenges.

Chem Rev. 2018-4-11

[9]
Kohn-Sham Decomposition in Real-Time Time-Dependent Density-Functional Theory: An Efficient Tool for Analyzing Plasmonic Excitations.

J Chem Theory Comput. 2017-10-10

[10]
Atomically Precise Clusters of Noble Metals: Emerging Link between Atoms and Nanoparticles.

Chem Rev. 2017-6-6

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