Chiral and Achiral Crystal Structures of Au25 (PET)18 0 Reveal Effects of Ligand Rotational Isomerization on Optoelectronic Properties.

The crystal structures of 4 ligand-rotational isomers of Au25 (PET)18 are presented. Two new ligand-rotational isomers are revealed, and two higher-quality structures (allowing complete solution of the ligand shell) of previously solved Au25 (PET)18 clusters are also presented. One of the structures lacks an inversion center, making it the first chiral Au25 (SR)18 structure solved. These structures combined with previously published Au25 (SR)18 structures enable an analysis of the empirical ligand conformation landscape for Au25 (SR)18 clusters. This analysis shows that the dihedral angles within the PET ligand are restricted to certain observable values, and also that the dihedral angle values are interdependent, in a manner reminiscent of biomolecule dihedral angles such as those in proteins and DNA. The influence of ligand conformational isomerism on optical and electronic properties was calculated, revealing that the ligand conformations affect the nanocluster absorption spectrum, which potentially provides a way to distinguish between isomers at low temperature.

Effects of Nanowire Doping on Plasmon-Enhanced N2 Dissociation.

Doping a transition metal element into plasmonic systems can tune the optical properties of the system, which will potentially facilitate the plasmon-enhanced catalytic process. In this study, we applied the linear-response time-dependent density functional theory (LR-TDDFT) method with real-time electron dynamics and mean-field Ehrenfest dynamics methods to computationally investigate the effects of doping silver nanowires on plasmon-enhanced N2 dissociation. We calculated the absorption spectra for different doped systems, applied an external electric field to the system, and performed mean-field Ehrenfest dynamics to examine how plasmonic excitation will affect the N2 activation or dissociation. In addition, we also studied how the transition metal dopant affects the system's electronic structure and potential energy surface.

Effects of Static Electric Fields on the Excitations of Silver Nanowire Dimers.

We theoretically studied the introduction of static electric fields to Ag10 nanowire dimer systems, including the effects of this field on optical absorption characteristics and the orbitals responsible for these excitations. Linear-response time-dependent density functional theory computations were performed on three distinct dimer systems: end-to-end, parallel, and 90° angle dimer systems separated by a closest interparticle distance of 7.0 Å. The calculations were performed in the presence of a 0.1 V/Å electric field strength applied in the z and y directions. The orientation of the dimer system and the direction of the applied static electric field each play a significant role in the resulting absorption spectra and the electronic structure of the nanowires. As a result, a dimer system can exhibit a blue shift for the longitudinal excitation and a red shift for the transverse excitation in the presence of one direction of the static electric field but not for the other direction. Notably, the electron density shifts from one nanowire to the other in the presence of the static electric field. Changes in optical characteristics and electronic structure suggest that the usage of a static electric field with a particular spatial configuration of nanowires provides a way to tune the optical properties of the system.

Temperature-Controlled Selective Formation of Silver Nanoclusters and Their Transformation to the Same Product.

Herein, two atomically precise silver nanoclusters, Ag54 and Ag33, directed by inner anion templates (CrO4 2- and/or Cl-), are initially isolated as a mixed phase from identical reactants across a wide temperature range (20-80 °C). Interestingly, fine-tuning the reaction temperature can realize pure phase synthesis of the two nanoclusters; that is, a metastable Ag54 is kinetically formed at a low temperature (20 °C), whereas such a system is steered towards a thermodynamically stable Ag33 at a relatively high temperature (80 °C). Electrospray ionization mass spectrometry illustrates that the stability of Ag33 is superior to that of Ag54, which is further supported by density functional theory calculations. Importantly, the difference in structural stability can influence the pathway of 1,4-bis(pyrid-4-yl)benzene induced transformation reaction starting from Ag54 and Ag33. The former undergoes a dramatic breakage-reorganization process to form an Ag31 dimer (Ag31), while the same product can be also achieved from the latter following a noninvasive ligand exchange process. Both the Ag54 and Ag33 have the potential for further remote laser ignition applications. This work not only demonstrates how temperature controls the isolation of a specific phase, but also sheds light on the structural transformation pathway of nanoclusters with different stability.

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.

Theoretical Investigations on the Plasmon-Mediated Dissociation of Small Molecules in the Presence of Silver Atomic Wires.

Plasmonic nanoparticles can promote bond activation in adsorbed molecules under relatively benign conditions via excitation of the nanoparticle's plasmon resonance. As the plasmon resonance often falls within the visible light region, plasmonic nanomaterials are a promising class of catalysts. However, the exact mechanisms through which plasmonic nanoparticles activate the bonds of nearby molecules are still unclear. Herein, we evaluate Ag8-X2 (X = N, H) model systems via real-time time-dependent density functional theory (RT-TDDFT), linear response time-dependent density functional theory (LR-TDDFT), and Ehrenfest dynamics in order to better understand the bond activation processes of N2 and H2 facilitated by the presence of the atomic silver wire under excitation at the plasmon resonance energies. We find that dissociation is possible for both small molecules at high electric field strength. Activation of each adsorbate is symmetry- and electric field-dependent, and H2 activates at lower electric field strengths than N2. This work serves as a step toward understanding the complex time-dependent electron and electron-nuclear dynamics between plasmonic nanowires and adsorbed small molecules.

Effects of Field Strength and Silver Nanowire Size on Plasmon-Enhanced N2 Dissociation.

Dissociation of the nitrogen molecule via plasmon-enhanced catalysis using noble metal nanoparticles has been investigated both experimentally and computationally in recent years. However, the mechanism of plasmon-enhanced nitrogen dissociation is still not very clear. In this work, we apply theoretical approaches to examine the dissociation of a nitrogen molecule on atomically thin Agn nanowires (n = 6, 8, 10, 12) and a Ag19+ nanorod. Ehrenfest dynamics provides information about the motion of nuclei during the dynamics process and real-time TDDFT calculations show the electronic transitions and population of electrons over the first 10 s of fs time scale. The activation and dissociation of nitrogen are typically enhanced when the electric field strength increases. However, the enhancement is not always monotonic with field strength. As the length of the Ag wire increases, nitrogen is typically easier to dissociate and thus requires lower field strengths, even though the plasmon frequency is lower. The Ag19+ nanorod leads to faster dissociation of N2 than the atomically thin nanowires. Overall, our detailed study yields insights into the mechanisms involved in plasmon-enhanced N2 dissociation, as well as provides information about factors that can be used to improve adsorbate activation.

Understanding the Ligand-Dependent Photoluminescent Mechanism in Small Alkynyl-Protected Gold Nanoclusters.

Alkynyl-protected gold clusters have recently gained attention because they are more structurally versatile than their thiolate-protected counterparts. Despite their flexibility, however, a higher photoluminescent quantum yield (PLQY) has been observed experimentally compared to that of organically soluble thiolate-protected clusters. Previous experiments have shown that changing the organic ligand, or R group, in these clusters does not affect the geometric or electronic properties of the core, leading to a similar absorption profile. This article serves as a follow-up to those experiments in which the geometric, optical, and photoluminescent (PL) properties of Au22(ETP)18 are pieced together to find the photoluminescence mechanism. These properties are then compared between Au22(C≡CR)18 clusters where the ligand is changed from R = ETP to PA and ET (ETP = 3-ethynylthiophene, PA = phenylacetylene, and ET = 3-ethynyltoluene). As the theoretical results do not reproduce the same absorption profile among the different ligands as in the experiment, this article also presents a supplementary benchmark of the geometric and optical properties among the three ligands for different levels of theory. The calculations show that the photoluminescence mechanism with the ETP ligand results in ligand-to-metal-to-metal charge transfer (LMMCT), while PA and ET are likely a result of core-dominated fluorescence. The changes are the result of the Au(I) ring atoms as well as how the aromatic groups are connected to the cluster. Additionally, dispersion, solvent, and polarization functions are all important to creating an accurate chemical environment, but the most useful tool in these calculations is the use of a long-range-corrected exchange-correlation functional.

Analytical excited state gradients for time-dependent density functional theory plus tight binding (TDDFT + TB).

Understanding photoluminescent mechanisms has become essential for photocatalytic, biological, and electronic applications. Unfortunately, analyzing excited state potential energy surfaces (PESs) in large systems is computationally expensive, and hence limited with electronic structure methods such as time-dependent density functional theory (TDDFT). Inspired by the sTDDFT and sTDA methods, time-dependent density functional theory plus tight binding (TDDFT + TB) has been shown to reproduce linear response TDDFT results much faster than TDDFT, particularly in large nanoparticles. For photochemical processes, however, methods must go beyond the calculation of excitation energies. Herein, this work outlines an analytical approach to obtain the derivative of the vertical excitation energy in TDDFT + TB for more efficient excited state PES exploration. The gradient derivation is based on the Z vector method, which utilizes an auxiliary Lagrangian to characterize the excitation energy. The gradient is obtained when the derivatives of the Fock matrix, the coupling matrix, and the overlap matrix are all plugged into the auxiliary Lagrangian, and the Lagrange multipliers are solved. This article outlines the derivation of the analytical gradient, discusses the implementation in Amsterdam Modeling Suite, and provides proof of concept by analyzing the emission energy and optimized excited state geometry calculated by TDDFT and TDDFT + TB for small organic molecules and noble metal nanoclusters.

Crystal Structure and Optical Properties of a Chiral Mixed Thiolate/Stibine-Protected Au18 Cluster.

We report the first example of a chiral mixed thiolate/stibine-protected gold cluster, formulated as Au18(S-Adm)8(SbPh3)4Br2 (where S-Adm = 1-adamantanethiolate). Single crystal X-ray crystallography reveals the origin of chirality in the cluster to be the introduction of the rotating arrangement of Au2(S-Adm)3 and Au(S-Adm)2 staple motifs on an achiral Au13 core and the subsequent capping of the remaining gold atoms by SbPh3 and Br- ligands. Interestingly, the structure and properties of this new Au18 cluster are found to be different from other reported achiral Au18 clusters and the only other stibine-protected [Au13(SbPh3)8Cl4]+ cluster. Detailed analyses on the geometric and electronic structures of the new cluster are carried out to gain insights into its optical properties as well as reactivity and stability of such mixed monolayer-protected clusters.

Sulfide Boosting Near-Unity Photoluminescence Quantum Yield of Silver Nanocluster.

Silver nanoclusters have emerged as promising candidates for optoelectronic applications, but their room-temperature photoluminescence quantum yield (PLQY) is far from ideal to access cutting-edge device performance. Herein, two supertetrahedral silver nanoclusters with high PLQY in non-degassed solution at room temperature were constructed by interiorly supporting the core with multiple VO43- and E2- anions as structure-directing agents and exteriorly protecting the core with a rigid ligand shell of PhC≡C- and Ph2PE2- (E = S, Ag64-S; E = Se, Ag64-Se). Both clusters have similar outer Ag58 tetrahedral cages and [Ag6E4@(VO4)4] cores, forming a pair of comparable clusters to decrypt the origin of such a high PLQY, particularly in Ag64-S, where the PLQY reached up to 97%. The stronger suppression effect of inner sulfides for nonradiative decay is critical to boost the PLQY to near unity. Transient absorption spectroscopy is employed to confirm the phosphorescence nature. The quadruple-capping assembly mechanism involving Ag7 secondary building units on a Ag36 truncated tetrahedron was also established by collision-induced dissociation studies. This work not only provides a strategy of core engineering for the controlled syntheses of silver nanoclusters with high PLQY but also deciphers the origin of a near-unity PLQY, which lays a foundation for fabricating highly phosphorescent silver nanoclusters in the future.

Time-dependent density functional theory study of the optical properties of tetrahedral aluminum nanoparticles.

The plasmonic properties of tetrahedral aluminum nanoparticles have been investigated using time-dependent functional theory (TDDFT) calculations. The excitation energies are calculated for tetrahedral aluminum nanoparticles (Aln , n = 10-120) with different charge states. The BP86/DZ model is used to perform geometric optimization calculations for these clusters. The SAOP/DZ and LB94/DZ levels of theory have been used for the excitation energy calculations of these tetrahedral aluminum clusters. The absorption peaks are red-shifted upon increasing the size of the aluminum nanoparticles.

Effects of Diglyme on Au Nanocluster Formation: Mechanism, 1H NMR, and Bonding.

Recently, diglyme was applied as a solvent in the synthesis of a luminescent gold-thiolate nanocluster. However, the interactions between the diglyme and the gold nanocluster and the intrinsic mechanism of the diglyme-assisted nanocluster growth have not been examined. In this work, we use density functional theory (DFT) to propose a plausible pathway for diglyme-assisted Au(I)-thiolate synthesis; the reaction energies are found to be negative in every step. 1H NMR calculations are applied to characterize how the environment arising from different gold motifs affects the chemical shifts of the protons on diglyme, which experience strong downfield shifts. Extended transition state-natural orbitals for chemical valence (ETS-NOCV) theory is also utilized to examine the interactions between diglyme and gold clusters as well as a Au20(SR)15 nanocluster. Our work demonstrates that diglyme can play an important role in the synthetic mechanism yielding gold nanoclusters and provides insights into the diglyme-nanocluster binding motifs and resulting NMR chemical shifts.

Plasmon-induced excitation energy transfer in silver nanoparticle dimers: A real-time TDDFTB investigation.

Using real-time quantum dynamics calculations, we perform theoretical investigations of light-induced interactions and electronic excitation transfer in a silver nanoparticle dimer. Real-time time-dependent density functional tight-binding (RT-TDDFTB) calculations provide details of the quantum dynamical processes at an electronic/atomistic level with attosecond resolution. The computational efficiency of RT-TDDFTB allows us to examine electronic dynamics up to picosecond time scales. With time scales varying over six orders of magnitude, we provide insight into interactions between the nanoparticle and laser and between nanoparticles. Our results show that the coupling between nanoparticle monomers is dependent on the separation distance between the nanoparticles in the dimer. As the interparticle distance is varied, the dipole-dipole interactions and electronic excitation transfer mechanisms are markedly different. At large distances (from 50 to 20 Å), the energy transfer from NP1 to NP2 becomes more efficient as the interparticle distance decreases. The total dipole moment of the Ag14 nanoparticle dimer increases linearly at an interparticle distance of 20 Å and reaches its maximum after 1.2 ps. The electronic excitation transfer is also the most efficient at 20 Å. At short distances, back-transfer effects reduce the ability of the dimer and NP1 to accept energy from the incident electric field. We attribute the distance-dependent features of the nanoparticle dimer to the beating between the laser acting on NP1 and the back transfer from NP2 to NP1.

An Ultrastable 155-Nuclei Silver Nanocluster Protected by Thiacalix[4]arene and Cyclohexanethiol for Photothermal Conversion.

Thiacalix[4]arenes have emerged as a family of macrocyclic ligands to protect metal nanoparticles, but it remains a great challenge to solve the mystery of their structures at the atomic level, especially for those larger than 2 nm. Here, we report the largest known mixed-valence silver nanocluster [Ag155 (CyS)40 (TC4A)5 Cl2 ] (Ag155) protected by deprotonated cyclohexanethiol (CySH) and macrocyclic ligand p-tert-butylthiacalix[4]arene (H4 TC4A). Its single-crystal structure consists of a metallic core of four concentric shells, Ag13 @Ag42 @Ag30 @Ag70 , lined with a organic skin of 40CyS- and 5TC4A4- and 2Cl- . Ag155 manifests an unusual pseudo-5-fold symmetry dictated by the intrinsic metal atom packing and the regioselective distribution of mixed protective ligands. This work not only reveals a macrocyclic ligand effect on the formation of a large silver nanocluster, but also provides a new structural archetype for comprehensively perceiving their interface and metal kernel structures.

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.

Correction: Analysis and visualization of energy densities. I. Insights from real-time time-dependent density functional theory simulations.

Correction for 'Analysis and visualization of energy densities. I. Insights from real-time time-dependent density functional theory simulations' by Junjie Yang et al., Phys. Chem. Chem. Phys., 2020, 22, 26838-26851, DOI: .

Real-Time Electron Dynamics Study of Plasmon-Mediated Photocatalysis on an Icosahedral Al13-1 Nanocluster.

Nitrogen bond dissociation is one of the important steps in the Haber-Bosch process, where N2 is catalytically converted to NH3; however, the dissociation of the nitrogen triple bond is difficult to achieve. In this study, we investigate the possibility of nitrogen activation using plasmonic excitation of an icosahedral aluminum nanocluster. Real-time time-dependent density functional theory is employed to study the electron dynamics of the Al13-1 and [Al13N2]-1 systems. Step and trapezoidal electric fields with field strengths of 0.001 and 0.01 au and different polarization directions are applied to the systems, and the electron dynamics are analyzed. Because the occupation of nitrogen antibonding orbitals could potentially activate the N-N bond, we investigated the single-particle electronic transitions corresponding to an excitation from an occupied (O) to virtual (V) molecular orbitals (POV) of [Al13N2]-1. We found that N2 antibonding orbitals are more likely to become populated with stronger fields and also by using off-resonance fields.

Theoretical Insights into Excitation-Induced Oxygen Activation on a Tetrahedral Ag8 Cluster.

Research on small-molecule dissociation on plasmonic silver nanoparticles is on the rise. Herein, we investigate the effect of various parameters of light, i.e., field strength, polarization direction, and energy of oscillation, on the dynamics of oxygen upon photoexcitation of the O2@Ag8 composite using real-time time-dependent density functional theory calculations with Ehrenfest dynamics. From our excited-state dynamics calculations, we found that increasing the strength of the external electric field brings a significant contribution to the O-O dissociation. In addition, the polarization direction of the incident light becomes important, especially at weaker field strengths. The light that is polarized along the direction of charge transfer from the metal to adsorbate and the light that is polarized along the long axis of molecular oxygen were found to enhance the bond breaking of O2 significantly. We also found that at the weakest electric field strength, the oxygen molecule stays adsorbed to the silver cluster when the incident light resonates with low-energy excited states and desorbs away from the metal cluster with high-energy excitations. With strong electric fields, oxygen either desorbs or dissociates.

Deciphering the dual emission in the photoluminescence of Au14Cd(SR)12: A theoretical study using TDDFT and TDDFT + TB.

Determining excited state processes for small nanoclusters, specifically gold, aids in our ability to fine-tune luminescent materials and optical devices. Using TDDFT and TDDFT + TB, we present a detailed theoretical explanation for the dual emission peaks displayed in Au14Cd(S-Adm)12 (Adm = adamantane). As dual emission is relatively rare, we decipher whether the mechanism originates from two different excited states or from two different minima on the same excited state surface. This unique mechanism, which proposes that the dual emission results from two minima on the first excited state, stems from geometrical changes in the bi-tetrahedron core during the emission process.