Characterization of Pt-doping effects on nanoparticle emission: a theoretical look at Au24Pt(SH)18 and Au24Pt(SC3H7)18.

Developments in nanotechnology have made the creation of functionalized materials with atomic precision possible. Thiolate-protected gold nanoclusters, in particular, have become the focus of study in literature as they possess high stability and have tunable structure-property relationships. In addition to adjustments in properties due to differences in size and shape, heteroatom doping has become an exciting way to tune the properties of these systems by mixing different atomic d characters from transition metal atoms. Au24Pt(SR)18 clusters, notably, have shown incredible catalytic properties, but fall short in the field of photochemistry. The influence of the Pt dopant on the photoluminescence mechanism and excited state dynamics has been investigated by a few experimental groups, but the origin of the differences that arise due to doping has not been clarified thoroughly. In this paper, density functional theory methods are used to analyze the geometry, optical and photoluminescent properties of Au24Pt(SR)18 in comparison with those of [Au25(SR)18]1-. Furthermore, as these clusters have shown slightly different geometric and optical properties for different ligands, the analysis is completed with both hydrogen and propyl ligands in order to ascertain the role of the passivating ligands.

Toward quantitative electronic structure in small gold nanoclusters.

Ligand-protected gold nanoclusters (AuNCs) feature a dense but finite electronic structure that can be rationalized using qualitative descriptions such as the well-known superatomic model and predicted using quantum chemical calculations. However, the lack of well-resolved experimental probes of a AuNC electronic structure has made the task of evaluating the accuracy of electronic structure descriptions challenging. We compare electronic absorption spectra computed using time-dependent density functional theory to recently collected high resolution experimental spectra of Au9(PPh3)8 3+ and Au8(PPh3)7 2+ AuNCs with strikingly similar features. After applying a simple scaling correction, the computed spectrum of Au8(PPh3)7 2+ yields a suitable match, allowing us to assign low-energy metal-metal transitions in the experimental spectrum. No similar match is obtained after following the same procedure for two previously reported isomers for Au9(PPh3)8 3+, suggesting either a deficiency in the calculations or the presence of an additional isomer. Instead, we propose assignments for Au9(PPh3)8 3+ based off of similarities Au8(PPh3)7 2+. We further model these clusters using a simple particle-in-a-box analysis for an asymmetrical ellipsoidal superatomic core, which allows us to reproduce the same transitions and extract an effective core size and shape that agrees well with that expected from crystal structures. This suggests that the superatomic model, which is typically employed to explain the qualitative features of nanocluster electronic structures, remains valid even for small AuNCs with highly aspherical cores.

Impact of Ligands on Structural and Optical Properties of Ag29 Nanoclusters.

A ligand exchange strategy has been employed to understand the role of ligands on the structural and optical properties of atomically precise 29 atom silver nanoclusters (NCs). By ligand optimization, ∼44-fold quantum yield (QY) enhancement of Ag29(BDT)12-x(DHLA)x NCs (x = 1-6) was achieved, where BDT and DHLA refer to 1,3-benzene-dithiol and dihydrolipoic acid, respectively. High-resolution mass spectrometry was used to monitor ligand exchange, and structures of the different NCs were obtained through density functional theory (DFT). The DFT results from Ag29(BDT)11(DHLA) NCs were further experimentally verified through collisional cross-section (CCS) analysis using ion mobility mass spectrometry (IM MS). An excellent match in predicted CCS values and optical properties with the respective experimental data led to a likely structure of Ag29(DHLA)12 NCs consisting of an icosahedral core with an Ag16S24 shell. Combining the experimental observation with DFT structural analysis of a series of atomically precise NCs, Ag29-yAuy(BDT)12-x(DHLA)x (where y, x = 0,0; 0,1; 0,12 and 1,12; respectively), it was found that while the metal core is responsible for the origin of photoluminescence (PL), ligands play vital roles in determining their resultant PLQY.

Luminescence and Electron Dynamics in Atomically Precise Nanoclusters with Eight Superatomic Electrons.

The [Au25(SR)18]- and [Au13(dppe)5Cl2]3+ [dppe = 1,2-bis(diphenylphosphino)ethane] nanoclusters both possess a 13-atom icosahedral core with 8 delocalized superatomic electrons (8e), but their emission properties and time-resolved electron dynamics differ significantly. In this work, experimental photoluminescence and photoluminescence decay measurements are combined with time-dependent density functional theory calculations of radiative and nonradiative decay properties and lifetimes to elucidate the similarities and differences in the emission of these two nanoclusters with similar cores. In this work, the photodynamic properties of [Au13(dppe)5Cl2]3+ are elucidated theoretically for the first time. [Au13(dppe)5Cl2]3+ exhibits a single strong emission peak compared to the weaker bimodal luminescence of [Au25(SR)18]- (modeled here as [Au25(SH)18]-). The strongly emissive state is found to arise from deexcitation out of the S1 state, similar to what is seen for [Au25(SH)18]-. Both theory and experiment exhibit microsecond lifetimes for this state. Transient absorption measurements and theoretical calculations demonstrate that the excited-state lifetimes for higher excited states are typically less than 1 ps. The decay times for the higher excited states of [Au13(dppe)5Cl2]3+ and its model compound [Au13(pe)5Cl2]3+ [pe = 1,2-bis(phosphino)ethane] are observed to be shorter than the lifetimes of the corresponding states of [Au25(SR)18]-; this occurs because the energy gap separating degenerate sets of unoccupied orbitals is only ∼0.2 eV in [Au13(dppe)5Cl2]3+ compared to a ∼0.6 eV energy gap in [Au25(SH)18]-.

Theoretical Investigation of Water Oxidation Mechanism on Pure Manganese and Ca-Doped Bimetal Oxide Complexes.

Understanding the role of Ca2+ ion in the oxygen-evolving complex of photosystem II is essential to design commercially viable and efficient water oxidation catalysts. To this end, small pure manganese oxide and calcium-doped manganese oxide model complexes saturated with water-derived ligands are investigated in this work. Density functional theory calculations are performed to investigate the water oxidation process on Mn2(µ-OH)(µ-O)(H2O)3(OH)5 (Mn2O4·6H2O) and CaMnO(µ-OH)2(H2O)5(OH)2 (CaMnO3·7H2O) complexes. Many reaction pathways are considered, and the three lowest energy water oxidation mechanisms on CaMnO3·7H2O have highest reaction energy steps of 1.37, 1.67, and 1.81 eV compared to the highest reaction energy step of 2.25 eV for the lowest energy mechanism of the pure Mn2O4·6H2O complex. Doping of the manganese dimer complex with calcium decreases the highest reaction energy of the water oxidation process. Consequently, the inclusion of calcium appears to improve the catalyst's efficiency for water splitting.

Connections Between Theory and Experiment for Gold and Silver Nanoclusters.

Ligand-stabilized gold and silver nanoparticles are of tremendous current interest in sensing, catalysis, and energy applications. Experimental and theoretical studies have closely interacted to elucidate properties such as the geometric and electronic structures of these fascinating systems. In this review, the interplay between theory and experiment is described; areas such as optical absorption and doping, where the theory-experiment connections are well established, are discussed in detail; and the current status of these connections in newer fields of study, such as luminescence, transient absorption, and the effects of solvent and the surrounding environment, are highlighted. Close communication between theory and experiment has been extremely valuable for developing an understanding of these nanocluster systems in the past decade and will undoubtedly continue to play a major role in future years.

Theoretical Insights into the Origin of Photoluminescence of Au25(SR)18(-) Nanoparticles.

Understanding fundamental behavior of luminescent nanomaterials upon photoexcitation is necessary to expand photocatalytic and biological imaging applications. Despite the significant amount of experimental work into the luminescence of Au25(SR)18(-) clusters, the origin of photoluminescence in these clusters still remains unclear. In this study, the geometric and electronic structural changes of the Au25(SR)18(-) (R = H, CH3, CH2CH3, CH2CH2CH3) nanoclusters upon photoexcitation are discussed using time-dependent density functional theory (TD-DFT) methods. Geometric relaxations in the optimized excited states of up to 0.33 Å impart remarkable effects on the energy levels of the frontier orbitals of Au25(SR)18(-) nanoclusters. This gives rise to a Stokes shift of 0.49 eV for Au25(SH)18(-) in agreement with experiments. Even larger Stokes shifts are predicted for longer ligands. Vibrational frequencies in the 75-80 cm(-1) range are calculated for the nuclear motion involved in the excited-state nuclear relaxation; this value is in excellent agreement with vibrational beating observed in time-resolved spectroscopy experiments. Several excited states around 0.8, 1.15, and 1.25 eV are calculated for the Au25(SH)18(-) nanocluster. Considering the typical underestimation of DFT excitation energies, these states are likely responsible for the emission observed experimentally in the 1.15-1.55 eV range. All excited states arise from core-based orbitals; charge-transfer states or other "semi-ring" or ligand-based states are not implicated.

Strong Tunable Visible Absorption Predicted for Polysilo-acenes Using TDDFT Calculations.

The optical properties of polysilo-acenes with two to six fused rings are studied using time-dependent density functional theory. We show that there are three spectral features in the absorption spectra analogous to α, ß, and p-band peaks known for carbon-based acenes. The ß peak is the most prominent feature in each spectrum, which appears in the visible region. Both α and ß peaks originate due to identical transitions that are polarized along the long axis of the system. The constructive interaction of quasi-degenerate configurations gives rise to the strong ß peak, while their destructive interaction results in the α peak with a low oscillator strength. Because the constructive interaction of configurations is characteristic of plasmons in acenes and noble metal nanoparticles, the ß peak can be identified as plasmonic for polysilo-acenes. The strong visible absorption and the potential for use in existing Si-technology affirm the interest in polysilo-acenes.