Density-functional tight-binding for phosphine-stabilized nanoscale gold clusters

Vuong, Van Quan; Madridejos, Jenica Marie L.; Aradi, Bálint; Sumpter, Bobby G.; Metha, Gregory F.; Irle, Stephan

doi:10.1039/d0sc04514d

Cited by 21 publications

(33 citation statements)

References 95 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

Section: Quantum Chemical Calculationsmentioning

confidence: 99%

“…[334] Following the development of the DFTB parameters for Au-P interactions, the simulations of ground-state properties such as IR and Raman spectra of very large phosphine-stabilized clusters can be made 1000× faster than before. Figure 15b shows the optimized geometry of Au 108 S 24 (PPh 3 ) 16 and the predicted far-IR spectra calculated using the DFTB2/auorg 𝛼' developed by Vuong et al [328]…”

Section: Simulation Of Far-infrared and Raman Spectroscopymentioning

confidence: 99%

“…[ 274 ] Recently, tight‐binding parameters for the Au–P interactions were generated and tested. [ 328 ] One of the applied benchmarks was the analysis of ligand bond dissociation of [Au 8 (PPh 3 ) 8 ] 2+ compared with DFT ( Figure 15 a ). This work demonstrated that using these parameters in DFTB formalism, ligand removal energy pathways can be calculated with computational ease for any phosphine‐stabilized Au cluster that is commonly de‐ligated for catalytic applications.…”

Section: Quantum Chemical Calculationsmentioning

confidence: 99%

“…Figure 15b shows the optimized geometry of Au 108 S 24 (PPh 3 ) 16 and the predicted far‐IR spectra calculated using the DFTB2/auorg α ’ developed by Vuong et al. [ 328 ]…”

Section: Quantum Chemical Calculationsmentioning

confidence: 99%

“…The recent development of the density functional tight‐binding parameters for the Au–P interaction has paved the way for faster calculation of ground‐state properties such as geometric and electronic structures and energetics, alongside the simulation of infrared spectra for phosphine‐stabilized Au clusters. [ 328 ] The accelerated calculation of the optical properties of these nanoclusters using time‐dependent DFTB could soon be the standard as the simulated absorption spectra of the large Au 70 S 20 (PPh 3 ) 12 and Au 108 S 24 (PPh 3 ) 16 clusters have recently been reported. [ 346 ] Likewise, the development of tight‐binding parameters involving the interaction of Au and P with different substrate surfaces like titania is necessary to further improve material design and reaction tunability of cluster‐based heterogeneous catalysts.…”

Section: Perspective and Future Prospectsmentioning

confidence: 99%

See 4 more Smart Citations

A Review of State of the Art in Phosphine Ligated Gold Clusters and Application in Catalysis

et al. 2022

Self Cite

View full text Add to dashboard Cite

Atomically precise gold clusters are highly desirable due to their well-defined structure which allows the study of structure-property relationships. In addition, they have potential in technological applications such as nanoscale catalysis. The structural, chemical, electronic, and optical properties of ligated gold clusters are strongly defined by the metal-ligand interaction and type of ligands. This critical feature renders gold-phosphine clusters unique and distinct from other ligand-protected gold clusters. The use of multidentate phosphines enables preparation of varying core sizes and exotic structures beyond regular polyhedrons. Weak gold-phosphorous (Au-P) bonding is advantageous for ligand exchange and removal for specific applications, such as catalysis, without agglomeration. The aim of this review is to provide a unified view of gold-phosphine clusters and to present an in-depth discussion on recent advances and key developments for these clusters. This review features the unique chemistry, structural, electronic, and optical properties of gold-phosphine clusters. Advanced characterization techniques, including synchrotron-based spectroscopy, have unraveled substantial effects of Au-P interaction on the composition-, structure-, and size-dependent properties. State-of-the-art theoretical calculations that reveal insights into experimental findings are also discussed. Finally, a discussion of the application of gold-phosphine clusters in catalysis is presented.

show abstract

Section: Quantum Chemical Calculationsmentioning

confidence: 99%

Section: Simulation Of Far-infrared and Raman Spectroscopymentioning

confidence: 99%

Section: Quantum Chemical Calculationsmentioning

confidence: 99%

“…Figure 15b shows the optimized geometry of Au 108 S 24 (PPh 3 ) 16 and the predicted far‐IR spectra calculated using the DFTB2/auorg α ’ developed by Vuong et al. [ 328 ]…”

Section: Quantum Chemical Calculationsmentioning

confidence: 99%

Section: Perspective and Future Prospectsmentioning

confidence: 99%

See 3 more Smart Citations

A Review of State of the Art in Phosphine Ligated Gold Clusters and Application in Catalysis

et al. 2022

Self Cite

View full text Add to dashboard Cite

show abstract

Recent Advances in Ligand Engineering for Gold Nanocluster Catalysis: Ligand Library, Ligand Effects and Strategies

Wang

Chen

Tang

2023

Chemistry An Asian Journal

View full text Add to dashboard Cite

Advances in new ligands in the last decade facilitated in‐depth studies on the property‐relationship of gold nanoclusters and promoted the rational synthesis and related applications of such materials. Currently, more and more new ligands are being explored; thus, the ligand library of AuNCs is being expanded fast, which also enables investigation of ligand effects of AuNCs via direct comparison of different ligating shell with the identical gold core. It is now widely accepted that ligands influence the properties of AuNCs enormously including stability, catalysis, photoluminescence among others. These studies inspired ligand engineering of AuNCs. One of the goals for ligand engineering is to develop ligated AuNC catalysts in which the ligands are able to exert big‐enough influence on electronic and steric control over catalysis as in a transition‐metal or an enzyme system. Although increasing attention is paid to the further expansion of ligand library, the investigation of design principles and strategies regarding ligands are still in their infant stage. This review summarizes the ligands for AuNC synthesis, the ligand effects on stability and catalysis, and recently developed strategies in promoting AuNC catalytic performance via ligand manipulation.

show abstract

Computational Modeling of 4d and 5d Transition Metal Catalysts

Urquhart¹,

Tuttle²

2024

Comprehensive Computational Chemistry

View full text Add to dashboard Cite

Density-functional tight-binding for phosphine-stabilized nanoscale gold clusters

Abstract: We report a parameterization of the density-functional tight-binding (DFTB) method for the accurate prediction of molecular, electronic and vibrational structure of phosphine-ligated nanoscale gold clusters, metalloids, and gold surfaces.

Cited by 21 publications

References 95 publications

A Review of State of the Art in Phosphine Ligated Gold Clusters and Application in Catalysis

A Review of State of the Art in Phosphine Ligated Gold Clusters and Application in Catalysis

Recent Advances in Ligand Engineering for Gold Nanocluster Catalysis: Ligand Library, Ligand Effects and Strategies

Computational Modeling of 4d and 5d Transition Metal Catalysts

Contact Info

Product

Resources

About