This study addresses how ligands module the structure and electronic optical properties of a large set experimentally known anionic thiolate-protected gold clusters, Au25(SR)18[1−]. Starting from experimental crystal structure, computational density functional theory calculations reveal that low-polarity R groups do not disturb Au25S18 framework significantly, such inversion symmetry(Ci) crystalline state is retained. In case p-thiolphenolate ligands, p-SPhX, major distortion framework,...

The structure of the Au15-thiolate cluster has been elucidated using a DFT approach, and it is demonstrated to comprise Au4-tetrahedron core protected solely by combination two concatenated staple motifs. longer motif efficiently wraps core, threads shorter one. structural assignment supported comparison powder X-ray diffraction pattern and, via time dependent-DFT calculations, optical chiroptical (CD) absorption spectra. calculated CD spectrum features characteristic strong peak centered at...

This report addresses a density functional theory study of the vibrational normal modes small-sized thiolate-protected gold clusters. Calculated far-infrared (far-IR) and low-frequency Raman spectra established clusters (4, 12, 18, 19, 20, 24, 25 Au atoms) show characteristic peaks in range 20–350 cm–1 that can be attributed to breathing mode core, Au–S–Au bending Au–S stretching modes. It was found as cluster size increases Au13 Au25 emerges. reveals both systematic specific characteristics...

The structure of the recently discovered Au130-thiolate and -dithiolate clusters is explored in a combined experiment-theory approach. Rapid electron diffraction scanning/transmission microscopy (STEM) enables atomic-resolution imaging gold core comparison with density functional theory (DFT)-optimized realistic models. results are consistent 105-atom truncated-decahedral protected by 25 short staple motifs, incorporating disulfide bridges linking dithiolate ligands. optimized also accounts,...

The structure and bonding of the gold-subhalide compounds Au144Cl60[z] are related to those ubiquitous thiolated gold clusters, or Faradaurates, by iso-electronic substitution thiolate chloride. Exact I-symmetry holds for [z] = [2+,4+] charge-states, in accordance with new electrospray mass spectrometry measurements predicted electron shell filling. high symmetry facilitates analysis global as well network, some striking results.

The structure and optical properties of a set R-1,1′-binaphthyl-2,2′-dithiol (R-BINAS) monosubstituted A-Au38(SCH3)24 clusters are studied by means time dependent density functional theory (TD-DFT). While it was proposed earlier that BINAS selectively binds to monomer motifs (SR-Au-SR) covering the Au23 core, our calculations suggest binding mode bridges two dimer (SR-Au-SR-Au-RS) motifs. more stable isomers show negligible distortion induced adsorption on Au38(SCH3)24 cluster which is...

The structure of penta-graphene (penta-C), an irregular pentagonal two-dimensional (2D) structure, has been predicted recently. In this communication we carried out a dispersion-corrected density functional theory (DFT-D) study the penta-C doped with Si, Ge and Sn atoms its related hydrogenated structures (H-penta-C-X). We predict various new as thermally stable based on Born-Oppenheimer molecular dynamics (BOMD) calculations. Moreover, their dynamical stability is attested by phonon...

Silver tetrahedral nanoparticles (NP) were synthesized using the inert gas condensation technique. We performed morphological and optical characterization of (NPs) atomic force microscopy (AFM), mass spectroscopy (MS), UV−visible spectroscopy. The Ag NPs produced by modified magnetron sputtering, followed thermalization in a high pressure zone. Along synthesis process, size was controlled through handling flow (Ar He), power, length aggregation optimized parameters to obtain peak on...

Recently, the X-ray determined structure of thiolated Au18 cluster has been reported. In this communication, we addressed a study structures and chiroptical properties doped with up to ten Ag atoms, which have calculated by Time Dependent Density Functional Theory (TD-DFT). The number atoms was steadily varied more stable isomers showed optical Circular Dichroism (CD) spectra distinct from that found for parent cluster. Doping than four results in enhancement oscillator strength HOMO-LUMO...

The effect of chiral and achiral ligands protecting the inner Au9 core Au18(SR)14 cluster is studied based on density functional theory (DFT) its corrected long-range interaction (DFT-D) approach. It was found that electronic properties (energy levels) depend specific ligands, which induce distinct distortions Au-S framework. However, substitution S-c-C6H11 as SCH3 may be considered to correct given obtained resemblance displayed bonding, optical chiroptical properties. A further comparison...

Thiolated gold clusters (TGCs) have received a lot of attention in the nanoscience field last decade because their potential applications that include catalysis, image diagnosis, photovoltaics, nanomedicine, and so forth. Their study has been fueled by development new synthesis, separation, analysis methods experimental side algorithms are able to propose more reliable initial structures during theoretical predictions. Till date, there than 70 calculated/synthesized structures, displaying...

N ‐Acetylneuraminic acid (sialic acid, Neu5Ac) has recently gained interest as a potential marker for variety of pathophysiological processes, although no Raman study been reported this important biomolecule. In paper, the vibrational properties Neu5Ac were studied by means Raman, surface‐enhanced scattering (SERS), and density functional theory calculations. By adsorption on silver nanoparticle surface, strongly enhanced intensities are obtained, allowing easy measurement small amounts...

Marks decahedron constitutes the core of thiolated Au₁₈₇ cluster.

The protected noble-metal structures comprising 145 metal-atom sites and 60 ligands are among the frequently identified larger metal-cluster systems exploited in many avenues of research. Herein we report a comparative electrospray ionization-mass spectrometry (ESI-MS) investigation 60-fold thiolated Au144 CuAu144 clusters, various positive charge-states, conjunction with density-functional theoretical (DFT) analysis based upon icosahedral Pd145-structure-type applicable to these systems....

Expanding the versatility of well‐defined clusters is a fundamental issue in design functional nanostructures. In this sense, concept super atoms allows us to gain deeper understanding and rationalization different properties metallic by invoking more familiar aspects. Recently, appear be intimately connected other relevant tools great chemical significance which enhance rational superatomic mimicking complex structures networks. Here, we expect account for research efforts from Latin...

Most of the studies devoted to thiolated gold clusters suppose that their core and Au-S framework do not suffer from distortion independently protecting ligands (-SR) it is assumed as correct simplify ligand SCH3. In this work delivered a systematic study structure vibrational properties (IR Raman) Au18(SR)14 cluster. The pursued goal understand dependency displayed Au18 cluster with type. A set six was considered during calculations based on density functional theory (DFT) in its...

This report contains a theoretical study on the atomic structure and normal modes of , clusters based density functional theory with generalised gradient approximations. It is shown that their calculated infrared (IR) spectra have features, which allow to distinguish them. Therefore, it was found Ag–S stretching CH3 umbrella are intense in IR spectrum cluster.

The interactions between functionalized noble-metal particles in an aqueous solution are central to applications relying on controlled equilibrium association. Herein, we obtain the potentials of mean force (PMF) for pair-interactions gold nanoparticles (AuNPs) physiological saline. These results based upon >1000 ns experiments silico all-atom model systems under and non-equilibrium conditions. Four types functionalization built by coating each globular Au144 cluster with 60 thiolate groups:...

A systematic study of bonding and bands structures armchair, zigzag chiral black phosphorus nanotubes is reported.

We present a [Au7(SR)7] ring as new type of protection ligand in atomic structure Au15(SR)13 nanocluster for the first time based on model developed to understand how interfacial interaction dictates structures motifs and gold cores thiolate-protected nanoclusters. This shows tetrahedral Au4 core protected by one two [Au2(SR)3] "staple" motifs. Density functional theory (DFT) calculations show that newly predicted (R = CH3/Ph) has lower energy 0.24/0.68 eV than previously proposed isomers....

The structure of the recently synthesized mercaptosuccinic acid-protected Au6Ag7(SR)10 cluster has been elucidated by a DFT approach, following an isoelectronic substitution seven Au atoms Ag on [Au13(SR)10]+ cluster. After systematic search for lowest-energy isomers, it is demonstrated that its comprises one octahedral-like Ag6 core covered two monoatomic dimer motifs and Au2Ag1(SR)4 staple-like motif. This result confirms prefer inner (core) positions while are located surface motifs.