It is an obstacle to precisely manipulate a doped heteroatom into desired position in metal nanocluster. Herein, we overcome this difficulty obtain Pt1 Au37 (SCH2 Pht Bu)24 and Pt2 Au36 nanoclusters via controllably doping Pt atoms the kernels of Au38 . We reveal that asymmetrical one atom either cores elevates relative energy HOMO (highest occupied molecular orbital) accompanied by valence electron loss , compared with 14 electrons, while symmetrical two narrows HOMO-LUMO gap (LUMO: lowest...

Abstract It is extremely difficult to distinguish the contributions of different sites on surface and in inner a catalyst overall catalytic performance, as observed results reflect an ensemble average from almost all active sites. How do that seem be not directly involved process exactly contribute performance? Toward this goal, herein studies only provide fundamental insights into how alteration Au 8 n +4 (SR) 4 +8 clusters by structure can dramatically change intrinsic properties, where (...

Improving the fundamental understanding of basic structures ligand-protected gold nanoclusters is essential to their bottom-up synthesis as well further application explorations. The thiolate ligands that cover central metal core in staple motifs are vital for stability clusters. However, knowledge about geometrical and bonding characters has not been fully uncovered yet. In this work, density functional theory calculations molecular orbital analysis applied show Au atoms hypervalent....

Here we report a diachronic evolvement from tetra-icosahedral Au30Ag12(C[triple bond, length as m-dash]CR)24 to quasi-hcp (hexagonal close-packed) Au47Ag19(C[triple m-dash]CR)32 via one-step reduction, in which the size/structure conversion of two clusters is not typical Oswald growth process, but involves interface shrinking followed by core rearrangement and surface polymerization. has an aesthetic Au18Ag8 kernel that composed four interpenetrating Au10Ag3 icosahedra, while twisted Au19...

Reactive force field (Reaxff) is a powerful method, which employs bond order/bond length formulism to describe breaking and reformation. In this work, modification the order formula was made Reaxff parameters were re-optimized. The underlying idea of these modifications improve energy gradient. Better agreements dissociation potential curves with quantum mechanical obtained on basis aforementioned changes. simulation carried out gain understandings iso-octane pyrolysis. apparent rate...

ConspectusThe revelation of numerous thiolate-protected gold nanocluster (TP-AuNCs) structures, achieved through a blend theoretical predictions and experimental detection/validation, presents vast amount data for understanding the structural evolution these nanoclusters. Typically, clusters featured an internal core surrounded by external "staple" motifs SR[Au(SR)]x (x = 0, 1, 2, 3, ...) at various charge states. In this Account, we outline our Grand Unified Model (GUM) that elucidates...

Abstract It is an obstacle to precisely manipulate a doped heteroatom into desired position in metal nanocluster. Herein, we overcome this difficulty obtain Pt 1 Au 37 (SCH 2 Ph t Bu) 24 and 36 nanoclusters via controllably doping atoms the kernels of 38 . We reveal that asymmetrical one atom either cores elevates relative energy HOMO (highest occupied molecular orbital) accompanied by valence electron loss , compared with 14 electrons, while symmetrical two narrows HOMO–LUMO gap (LUMO:...

Thiolate-protected Au nanoclusters (AuNCs) have been widely studied in areas of catalysis, biosensors, and bioengineering. In real applications, e.g., catalytic reactions, the thiolate groups are normally partially detached. However, which easily detached how detachment ligands affects geometries electronic structures rarely studied. this work, we employed density functional theory calculations as well molecular orbital analysis to explore effect using nine thiolate-protected AuNCs examples....

The formation of the aromatic ring during polycyclic hydrocarbons (PAHs) remains controversial and experimental evidence is still lacking. Moreover, mechanism benzene from acetylene in gas phase has also puzzled organic chemists for decades. Here, ab initio molecular dynamics simulations electronic structure calculations provide compelling an unexpected competitive reaction pathway which formed through successive additions vinylidene. no collisions cause bond dissociation molecule this work....

Structural prediction of thiolate-protected gold nanoclusters (AuNCs) with diverse charge states can enrich the understanding this species. Untill now, number anion AuNCs is still deficient. In work, a series negative total charge, including [Au28(SR)17]-, [Au35(SR)20]-, [Au42(SR)23]-, [Au49(SR)26]-, and [Au56(SR)29]-, are designed. Following crystallized [Au23(SR)16]- prototype structure, inner core newly predicted clusters obtained through packing crossed Au7. Next, proper protecting...

Triangular Au3 and tetrahedral Au4 are key structural units in the face-centered cubic gold core of thiolate-protected nanoclusters. Understanding their stacking arrangements is essential for elucidating growth mechanisms these cores. In this study, we design two new isomers Au29(SR)19 nanoclusters via deliberately adjusting pattern based on grand unified model ring to show preferable packing arrangements. Among experimental isomer newly constructed Au29(SR)19, display three distinct...

The hydrated-proton structure is critical for understanding the proton transport in water. However, whether hydrated adopts Zundel or Eigen solution has been highly debated past several decades. Current experimental techniques cannot directly visualize dynamic structures situ , while available theoretical results on infrared (IR) spectrum derived from current configurational models fully reproduce and thus are unable to provide their precise structures. In this work, using <mml:math...

Abstract Ribosome methylation is important for life processes and mainly catalyzed by radical S‐Adenosylmethionine (SAM) enzymes. Two SAM molecules serve as the cofactor providing 5 ′‐deoxyadenosyl substrate activation methyl. Recently, Booker coworkers (Science 2011, 332, 604) proposed an alternative mechanism a pair of enzymes, RlmN Cfr, which respectively methylate C2 C8 adenosine 2503. Their deuterium labeling experiments reveal that methyl group does not transfer directly from to...

In this study, we examined the reaction between resonant i-C4H3 radical and C2H2. A network was constructed using CCSD(T)/CBS//M06-2X/6-311++G(d,p) dual level theory. Several undisclosed channels were first examined. Their necessities demonstrated by branching ratios. The shows that hydrogen elimination products, carbon–carbon bond-breaking four-membered rings, or six-membered rings may be possible products. To further examine which products are more preferred under different conditions, one...

Nanoscale confinement provides an ideal platform to rouse some exceptional reactions which cannot happen in the open space. Intuitively, H2 and H$_2$O react. Herein, through utilizing small-sized fullerenes (C$_{24}$, C$_{26}$, C$_{28}$, C$_{30}$) as nanoreactors, we demonstrate that a hyperhydrogenated water species, H$_4$O, can be easily formed using under ambient conditions by ab initio molecular dynamics simulations.The H$_4$O molecule rotates freely cavity of cages maintains its...