Combined experimental and computational study of the photoabsorption of the monodoped and nondoped nanoclusters Au24Pt(SR)18, Ag24Pt(SR)18, and Ag25(SR)18.

Assessing the accuracy of first-principles computational approaches is instrumental to predict electronic excitations in metal nanoclusters with quantitative confidence. Here we describe a validation study on the optical response of a set of monolayer-protected clusters (MPC). The photoabsorption spectra of Ag25(DMBT)18-, Ag24Pt(DMBT)182- and Au24Pt(SC4H9)18, where DMBT is 2,4-dimethylbenzenethiolate and SC4H9 is n-butylthiolate, have been obtained at low temperature and compared with accurate TDDFT calculations. An excellent match between theory and experiment, with typical deviations of less than 0.1 eV, was obtained, thereby validating the accuracy and reliability of the proposed computational framework. Moreover, an analysis of the TDDFT simulations allowed us to ascribe all relevant spectral features to specific transitions between occupied/virtual orbital pairs. The doping effect of Pt on the optical response of these ultrasmall MPC systems was identified and discussed.

Oxygen Promoted On-Surface Synthesis of Polyboroxine Molecules.

We present our findings on the on-surface synthesis of polyboroxine molecules derived from boroxine molecules precursors. This process is promoted by oxygen species present on the Au(111) surface: oxygen atoms facilitate the detachment of naphthalene units of trinaphthyl-boroxine molecules and bridge two unsaturated boroxine centers to form a boroxine-O-boroxine chemical motif. X-ray spectroscopic characterization shows that, as the synthesis process proceeds, it progressively tunes the electronic properties of the interface, thus providing a promising route to control the electron level alignment. .

Unrevealing the Nitrogen Elusive Chirality of 3-Sulfanyl and 3-Sulfinyl N-Tosyl Isoindolinones by ECD Spectra: An Experimental and Theoretical Investigation.

The nitrogen-hybridization/pyramidalization of two solvated N-tosylisoindolinone derivatives having chiral residues in adjacent (I) or adjacent and distal (II) position has been investigated by a theoretical-computational procedure based on Molecular Dynamics simulations and Quantum-Chemical calculations. After validation of our methodology in providing a reliable repertory of conformations by modeling the electronic circular dichroism (EDC) spectra, the electronic features associated with N-pyramidalization were further characterized through Natural Bond Order (NBO) analysis. Comparing against the N-geometry observed in crystal structures as a reference, our findings reveal that the presence of neighbouring chiral centers induces a more pronounced N-pyramidalization in solution than in the solid state, both in I and II. Furthermore, NBO analysis confirms that the N-lactam mostly retains the sp2 character but exhibits slight configurational distortion (ξI=13°; ξII=21°), which significantly influences the chiroptical activities observed in ECD spectra of I and II. This substantiates the N-lactams as configurationally stable chiral centers.

Dichroism of plasmonic chiral nanoalloys by rational design.

Time-dependent density functional theory (TDDFT) simulations are conducted on a series of chiral gold/silver alloy nanowires to explore whether silver doping can produce an enhancement of circular dichroism at the plasmon resonance in these systems, and to identify the quantum-mechanical origin of the observed effects. We find a strong plasmonic dichroism when one or two helixes of gold atoms are substituted by silver in a linear chiral nanotube, whose pure gold counterpart does not display any plasmonic dichroism, and we rationalize this finding in terms of "decoupling" the destructive interference of excitations in the pure gold nanotube via alloying. However, further attempts to increase the plasmonic dichroism by considering multi-shell gold nanowires in which one entire shell is doped with silver did not produce the desired effect, but rather a decrease in circular dichroism. We show that this latter result is due to a more severe destructive interference in the dipole excitation contributions, and suggest that further amplification should be possible in principle by properly tuning simultaneously the nanowire structure and chemical ordering.

Peeking into the Femtosecond Hot-Carrier Dynamics Reveals Unexpected Mechanisms in Plasmonic Photocatalysis.

Plasmonic-driven photocatalysis may lead to reaction selectivity that cannot be otherwise achieved. A fundamental role is played by hot carriers, i.e., electrons and holes generated upon plasmonic decay within the metal nanostructure interacting with molecular species. Understanding the elusive microscopic mechanism behind such selectivity is a key step in the rational design of hot-carrier reactions. To accomplish that, we present state-of-the-art multiscale simulations, going beyond density functional theory, of hot-carrier injections for the rate-determining step of a photocatalytic reaction. We focus on carbon dioxide reduction, for which it was experimentally shown that the presence of a rhodium nanocube under illumination leads to the selective production of methane against carbon monoxide. We show that selectivity is due to a (predominantly) direct hole injection from rhodium to the reaction intermediate CHO. Unexpectedly, such an injection does not promote the selective reaction path by favoring proper bond breaking but rather by promoting bonding of the proper molecular fragment to the surface.

Effects of Oxygen Adsorption on the Optical Properties of Ag Nanoparticles.

Plasmonic metal nanoparticles are efficient light harvesters with a myriad of sensing- and energy-related applications. For such applications, the optical properties of nanoparticles of metals such as Cu, Ag, and Au can be tuned by controlling the composition, particle size, and shape, but less is known about the effects of oxidation on the plasmon resonances. In this work, we elucidate the effects of O adsorption on the optical properties of Ag particles by evaluating the thermodynamic properties of O-decorated Ag particles with calculations based on the density functional theory and subsequently computing the photoabsorption spectra with a computationally efficient time-dependent density functional theory approach. We identify stable Ag nanoparticle structures with oxidized edges and a quenching of the plasmonic character of the metal particles upon oxidation and trace back this effect to the sp orbitals (or bands) of Ag particles being involved both in the plasmonic excitation and in the hybridization to form bonds with the adsorbed O atoms. Our work has important implications for the understanding and application of plasmonic metal nanoparticles and plasmon-mediated processes under oxidizing environments.

Electronic Structure of Pentagonal Carbon Nanocones: An ab Initio Study.

In this work, we investigate the electronic structure of a particular class of carbon nanocones having a pentagonal tip and C5v symmetry. The ground-state nature of the wave function for these structures can be predicted by the recently proposed generalized Hückel rule that extends the original Hückel rule for annulenes to this class of carbon nanocones. In particular, the structures here considered can be classified as closed-shell or anionic/cationic closed-shells, depending on the geometric characteristics of the cone. The goal of this work is to assess the relationship between the electronic configuration of these carbon nanocones and their ability to gain or lose an electron as well as their adsorption capability. For this, the geometry of these structures in the neutral or ionic forms, as well as systems containing either one lithium or fluorine atom, was optimized at the DFT/B3LYP level. It was found that the electron affinity, ionization potential, and the Li or F adsorption energy present an intimate connection to the ground-state wave function character predicted by the generalized Hückel rule. In fact, a peculiar oscillatory energy behavior was discovered, in which the electron affinity, ionization energy, and adsorption energies oscillate with an increase in the nanocone size. The reasoning behind this is that if the anion is closed-shell, then the neutral nanocone will turn out to be a good electron acceptor, increasing the electron affinity and lithium adsorption energy. On the other hand, in the case of a closed-shell cation, this means that the neutral nanocone will easily lose an electron, leading to a smaller ionization potential and higher fluorine adsorption energy.

A Resolution of Identity Technique to Speed up TDDFT with Hybrid Functionals: Implementation and Application to the Magic Cluster Series Au8n+4(SC6H5)4n+8 (n = 3-6).

The Resolution of Identity (RI) technique has been employed to speed up the use of hybrid exchange-correlation (xc) functionals at the TDDFT level using the Hybrid Diagonal Approximation. The RI has been implemented within the polTDDFT algorithm (a complex damped polarization method) in the AMS/ADF suite of programs. A speedup factor of 30 has been obtained with respect to a previous numerical implementation, albeit with the same level of accuracy. Comparison of TDDFT simulations with the experimental photoabsorption spectra of the cluster series Au8n+4(SR)4n+8(n = 3-6; R = C6H5) showed the excellent accuracy and efficiency of the method. Results were compared with those obtained via the more simplified and computationally cheaper TDDFT+TB and sTDDFT methods. The present method represents an accurate as well as computationally affordable approach to predict photoabsorption spectra of complex species, realizing an optimal compromise between accuracy and computational efficiency, and is suitable for applications to large metal clusters with sizes up to several hundreds of atoms.

Time Evolution of Plasmonic Features in Pentagonal Ag Clusters.

In the present work, we apply recently developed real-time descriptors to study the time evolution of plasmonic features of pentagonal Ag clusters. The method is based on the propagation of the time-dependent Schrödinger equation within a singly excited TDDFT ansatz. We use transition contribution maps (TCMs) and induced density to characterize the optical longitudinal and transverse response of such clusters, when interacting with pulses resonant with the low-energy (around 2-3 eV, A1) size-dependent or the high-energy (around 4 eV, E1) size-independent peak. TCMs plots on the analyzed clusters, Ag25+ and Ag43+ show off-diagonal peaks consistent with a plasmonic response when a longitudinal pulse resonant at A1 frequency is applied, and dominant diagonal spots, typical of a molecular transition, when a transverse E1 pulse is employed. Induced densities confirm this behavior, with a dipole-like charge distribution in the first case. The optical features show a time delay with respect to the evolution of the external pulse, consistent with those found in the literature for real-time TDDFT calculations on metal clusters.

What Contributes to the Measured Chiral Optical Response of the Glutathione-Protected Au25 Nanocluster?

The water-soluble glutathione-protected [Au25(GSH)18]-1 nanocluster was investigated by integrating several methodologies such as molecular dynamics simulations, essential dynamics analysis, and state-of-the-art time-dependent density functional theory calculations. Fundamental aspects such as conformational, weak interactions and solvent effects, especially hydrogen-bonds, were included and found to play a fundamental role in assessing the optical response of this system. Our analysis demonstrated not only that the electronic circular dichroism is extremely sensitive to the solvent presence but also that the solvent itself plays an active role in the optical activity of such system, forming a chiral solvation shell around the cluster. Our work demonstrates a successful strategy to investigate in detail chiral interfaces between metal nanoclusters and their environments, applicable, e.g., to chiral electronic interactions between clusters and biomolecules.

Probing Intermolecular H-Bonding Interactions in Cyanuric Acid Networks: Quenching of the N K-Edge Sigma Resonances.

The electronic characterization of the cyanuric acid both in gas phase and when embedded within an H-bonded scheme forming a monolayer on the Au(111) surface has been performed by means of X-ray Photoelectron Spectroscopy (XPS) and Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy. The experimental spectra at the N, O, and C K-edges have been assigned with the support of DFT calculations, and the combination between theory and experiment has allowed to us investigate the effect of the H-bonding intermolecular interaction on the spectra. In particular, the H-bond formation in the monolayer leads to a quenching of the N 1s NEXAFS resonances associated with transitions to the sigma empty orbitals localized on the N-H portion of the imide group. On the other hand, the π* empty states remain substantially unperturbed. From a computational point of view, it has been shown that the DFT-TP scheme is not able to describe the N 1s NEXAFS spectra of these systems, and the configuration mixing has to be included, through the TDDFT approach in conjunction with the range-separated XC CAM-B3LYP functional, to obtain a correct reproduction of the N 1s core spectra.

Optimization of density fitting auxiliary Slater-type basis functions for time-dependent density functional theory.

A new set of auxiliary basis function suitable to fit the induced electron density is presented. Such set has been optimized in order to furnish accurate absorption spectra using the complex polarizability algorithm of time-dependent density functional theory (TDDFT). An automatic procedure has been set up, able, thanks to the definition of suitable descriptors, to evaluate the resemblance of the auxiliary basis-dependent calculated spectra with respect to a reference. In this way, it has been possible to reduce the size of the basis set maximizing the basis set accuracy. Thanks to the choice to employ a collection of molecules for each element, such basis has proven transferable to molecules outside the collection. The final sets are therefore much more accurate and smaller than the previously optimized ones and have been already included in the database of the last release of the AMS suite of programs. The availability of the present new set will allow to improve drastically the applicability range of the polTDDFT method with higher accuracy and less computational effort.

Accurate Vertical Excitation Energies of BODIPY/Aza-BODIPY Derivatives from Excited-State Mean-Field Calculations.

We report a benchmark study of vertical excitation energies and oscillator strengths for the HOMO → LUMO transitions of 17 boron-dipyrromethene (BODIPY) structures, showing a large variety of ring sizes and substituents. Results obtained at the time-dependent density functional theory (TDDFT) and at the delta-self-consistent-field (ΔSCF) by using 13 different exchange correlation kernels (within LDA, GGA, hybrid, and range-separated approximations) are benchmarked against the experimental excitation energies when available. It is found that the time-independent ΔSCF DFT method, when used in combination with hybrid PBE0 and B3LYP functionals, largely outperforms TDDFT and can be quite competitive, in terms of accuracy, with computationally more costly wave function based methods such as CC2 and CASPT2.

A computational approach for modeling electronic circular dichroism of solvated chromophores.

The present study consists in a novel computational protocol to model the UV-circular dichroism spectra of solvated species. It makes use of quantum-chemical calculations on a series of conformations of a flexible chromophore or on a series of chromophore/solvent clusters extracted from molecular dynamic simulations. The protocol is described and applied to the aqueous cationic tripeptide GAG+ and to the aqueous neutral decapeptide (GVGVP)2 . The protocol has proven able to: (i) properly consider the conformational motion of solute in the given environment; (ii) give the actual statistical weight of each conformational state; (iii) provide a reliable quantum mechanical method able to reproduce the spectral features. Temperature effects on conformations and spectral properties are properly taken into account. The role of explicit solvent on the conformational analysis and the spectra calculation is discussed. The comparison of the calculated circular dichroism spectra with experimental ones recorded at different temperatures represents a strict validation test of the method.

Coupling between Plasmonic and Molecular Excitations: TDDFT Investigation of an Ag-Nanorod/BODIPY-Dye Interaction.

A time-dependent density functional theory (TDDFT) computational approach is employed to study the optical coupling between a plasmonic system (a Ag50 nanorod) and a fluorescent dye (BODIPY). It is found that the BODIPY dye can interact with a plasmonic system in a rather different and selective way according to the mutual orientation of the fragments. Indeed, (i) the plasmon excitation turns out to be sensitive to the presence of the BODIPY transition and (ii) this can lead to amplify or suppress the resonance accordingly to the relative orientation of the corresponding transition dipoles. To understand the coupling mechanism, we analyze the shape of the induced density in real space and the Individual Component Map of the Oscillator Strength (ICM-OS) plots and achieve a simple rationalization and insight on the origin and features of the coupling. The resulting possibility of understanding plasmon/fluorophore interactions by simple qualitative arguments opens the way to a rational design of hybrid (plasmon + dye) systems with the desired optical behavior.

Computational NEXAFS Characterization of Molecular Model Systems for 2D Boroxine Frameworks.

The electronic properties of 2D boroxine networks are computationally investigated by simulating the NEXAFS spectra of a series of molecular models, with or without morphologic defects, with respect to the ideal honeycomb structure. The models represent portions of an irregular 2D boroxine framework obtained experimentally, as supported by the Au(111) surface. The B K-edge NEXAFS spectra are calculated within the transition potential (TP) approximation (DFT-TP). The role of the Au(111) supporting surface on the spectral features has also been investigated by comparing the calculated spectra of a defect-rich model in its free-standing and supported form. The calculated NEXAFS spectra differ from the experimental ones, as the position of the main resonance does not match in the two cases. This finding could suggest the presence of a strong interaction of the 2D boroxine network with the Au substrate, which is not captured in the model calculations. However, good agreement between measured and calculated B K-edge NEXAFS spectra is obtained for a model system, namely, trihydroxy boroxine, in which the B atoms are less screened by the valence electrons compared to the B-B linked boroxine network models considered here. These results suggest catalytic activity in the gold substrate in promoting a weakening or even the breaking of the B-B bond, which is not revealed by calculations.

Continuum Electronic States: The Tiresia Code.

A multicenter (LCAO) B-spline basis is described in detail, and its capabilities concerning affording convergent solutions for electronic continuum states and wavepacket propagation are presented. It forms the core of the Tiresia code, which implements static-DFT and TDDFT hamiltonians, as well as single channel Dyson-DFT and Dyson-TDDFT descriptions to include correlation in the bound states. Together they afford accurate and computationally efficient descriptions of photoionization properties of complex systems, both in the single photon and strong field environments. A number of examples are provided.

Optical Activity of Metal Nanoclusters Deposited on Regular and Doped Oxide Supports from First-Principles Simulations.

We report a computational study and analysis of the optical absorption processes of Ag20 and Au20 clusters deposited on the magnesium oxide (100) facet, both regular and including point defects. Ag20 and Au20 are taken as models of metal nanoparticles and their plasmonic response, MgO as a model of a simple oxide support. We consider oxide defects both on the oxygen anion framework (i.e., a neutral oxygen vacancy) and in the magnesium cation framework (i.e., replacing Mg++ with a transition metal: Cu++ or Co++). We relax the clusters' geometries via Density-Functional Theory (DFT) and calculate the photo-absorption spectra via Time-Dependent DFT (TDDFT) simulations on the relaxed geometries. We find that the substrate/cluster interaction induces a broadening and a red-shift of the excited states of the clusters, phenomena that are enhanced by the presence of an oxygen vacancy and its localized excitations. The presence of a transition-metal dopant does not qualitatively affect the spectral profile. However, when it lies next to an oxygen vacancy for Ag20, it can strongly enhance the component of the cluster excitations perpendicular to the surface, thus favoring charge injection.

AgPd, AuPd, and AuPt Nanoalloys with Ag- or Au-Rich Compositions: Modeling Chemical Ordering and Optical Properties.

Bimetallic nanoparticles have a myriad of technological applications, but investigations of their chemical and physical properties are precluded due to their structural complexity. Here, the chemical ordering and optical properties of AgPd, AuPd, and AuPt nanoparticles have been studied computationally. One of the main aims was to clarify whether layered ordered phases similar to L11 one observed in the core of AgPt nanoparticles [Pirart J.; Nat. Commun.2019, 10, 1982] are also stabilized in other nanoalloys of coinage metals with platinum-group metals, or the remarkable ordering is a peculiarity only of AgPt nanoparticles. Furthermore, the effects of different chemical orderings and compositions of the nanoalloys on their optical properties have been explored. Particles with a truncated octahedral geometry containing 201 and 405 atoms have been modeled. For each particle, the studied stoichiometries of the Ag- or Au-rich compositions, ca. 4:1 for 201-atomic particles and ca. 3:1 for 405-atomic particles, corresponded to the layered structures L11 and L10 inside the monatomic coinage-metal skins. Density functional theory (DFT) calculations combined with a recently developed topological (TOP) approach [Kozlov S. M.; Chem. Sci.2015, 6, 3868-3880] have been performed to study the chemical ordering of the particles, whose optical properties have been investigated using the time-dependent DFT method. The obtained results revealed that the remarkable ordering L11 of inner atoms can be noticeably favored only in small AgPt particles and much less in AgPd ones, whereas this L11 ordering in analogous Au-containing nanoalloys is significantly less stable compared to other calculated lowest-energy orderings. Optical properties were found to be more dependent on the composition (concentration of two metals) than on the chemical ordering. Both Pt and Pd elements promote the quenching of the plasmon.

Predictive optical photoabsorption of Ag24Au(DMBT)18 - via efficient TDDFT simulations.

We report a computational study via time-dependent density-functional theory (TDDFT) methods of the photo-absorption spectrum of an atomically precise monolayer-protected cluster (MPC), the Ag24Au(DMBT)18 single negative anion, where DMBT is the 2,4-dimethylbenzenethiolate ligand. The use of efficient simulation algorithms, i.e., the complex polarizability polTDDFT approach and the hybrid-diagonal approximation, allows us to employ a variety of exchange-correlation (xc-) functionals at an affordable computational cost. We are thus able to show, first, how the optical response of this prototypical compound, especially but not exclusively in the absorption threshold (low-energy) region, is sensitive to (1) the choice of the xc-functionals employed in the Kohn-Sham equations and the TDDFT kernel and (2) the choice of the MPC geometry. By comparing simulated spectra with precise experimental photoabsorption data obtained from room temperature down to low temperatures, we then demonstrate how a hybrid xc-functional in both the Kohn-Sham equations and the diagonal TDDFT kernel at the crystallographically determined experimental geometry is able to provide a consistent agreement between simulated and measured spectra across the entire optical region. Single-particle decomposition analysis tools finally allow us to understand the physical reason for the failure of non-hybrid approaches.