Molecular Pseudorotation in Phthalocyanines as a Tool for Magnetic Field Control at the Nanoscale.

Metal phthalocyanines, a highly versatile class of aromatic, planar, macrocyclic molecules with a chelated central metal ion, are topical objects of ongoing research and particularly interesting due to their magnetic properties. However, while the current focus lies almost exclusively on spin-Zeeman-related effects, the high symmetry of the molecule and its circular shape suggests the exploitation of light-induced excitation of 2-fold degenerate vibrational states in order to generate, switch, and manipulate magnetic fields at the nanoscale. The underlying mechanism is a molecular pseudorotation that can be triggered by infrared pulses and gives rise to a quantized, small, but controllable magnetic dipole moment.

Symmetry- and gradient-enhanced Gaussian process regression for the active learning of potential energy surfaces in porous materials.

The theoretical investigation of gas adsorption, storage, separation, diffusion, and related transport processes in porous materials relies on a detailed knowledge of the potential energy surface of molecules in a stationary environment. In this article, a new algorithm is presented, specifically developed for gas transport phenomena, which allows for a highly cost-effective determination of molecular potential energy surfaces. It is based on a symmetry-enhanced version of Gaussian process regression with embedded gradient information and employs an active learning strategy to keep the number of single point evaluations as low as possible.

Stability and Reversible Oxidation of Sub-Nanometric Cu Metal Clusters: Integrated Experimental Study and Theoretical Modeling.

Sub-nanometer metal clusters have special physical and chemical properties, significantly different from those of nanoparticles. However, there is a major concern about their thermal stability and susceptibility to oxidation. In situ X-ray Absorption spectroscopy and Near Ambient Pressure X-ray Photoelectron spectroscopy results reveal that supported Cu clusters are resistant to irreversible oxidation at least up to 773 K, even in the presence of 0.

Mixed-metal nanoparticles: phase transitions and diffusion in Au-VO clusters.

Nanoparticles with diameters in the range of a few nanometers, consisting of gold and vanadium oxide, are synthesized by sequential doping of cold helium droplets in a molecular beam apparatus and deposited on solid carbon substrates. After surface deposition, the samples are removed and various measurement techniques are applied to characterize the created particles: scanning transmission electron microscopy (STEM) at atomic resolution, temperature dependent STEM and TEM up to 650 °C, energy-dispersive X-ray spectroscopy (EDXS) and electron energy loss spectroscopy (EELS). In previous experiments we have shown that pure VO nanoparticles can be generated by sublimation from the bulk and deposited without affecting their original stoichiometry.

Vibronic Coupling in Spherically Encapsulated, Diatomic Molecules: Prediction of a Renner-Teller-like Effect for Endofullerenes.

In the year 1933, Herzberg and Teller realized that the potential energy surface of a triatomic, linear molecule splits into two as soon as the molecule is bent. The phenomenon, later dubbed the Renner-Teller effect due to the detailed follow-up work of Renner on the subject, describes the coupling of a symmetry-reducing molecular vibration with degenerate electronic states. In this article, we show that a very similar type of nonadiabatic coupling can occur for certain translational degrees of freedom of diatomic, electronically degenerate molecules when trapped in a nearly spherical or cylindrical quantum confinement, e.

A Path Integral Molecular Dynamics Simulation of a Harpoon-Type Redox Reaction in a Helium Nanodroplet.

We present path integral molecular dynamics (PIMD) calculations of an electron transfer from a heliophobic Cs2 dimer in its (3Σu) state, located on the surface of a He droplet, to a heliophilic, fully immersed C60 molecule. Supported by electron ionization mass spectroscopy measurements (Renzler et al., , , 181101), this spatially quenched reaction was characterized as a harpoon-type or long-range electron transfer in a previous high-level study (de Lara-Castells et al.

Nonadiabatic Effects in the Molecular Oxidation of Subnanometric Cu Clusters.

The electronic structure of subnanometric clusters, far off the bulk regime, is still dominated by molecular characteristics. The spatial arrangement of the notoriously undercoordinated metal atoms is strongly coupled to the electronic properties of the system, which makes this class of materials particularly interesting for applications including luminescence, sensing, bioimaging, theranostics, energy conversion, catalysis, and photocatalysis. Opposing a common rule of thumb that assumes an increasing chemical reactivity with smaller cluster size, Cu clusters have proven to be exceptionally resistant to irreversible oxidation, i.

On the Stability of Cu Catalysts in Air Using Multireference Perturbation Theory.

An ab initio study of the interaction of O, the most abundant radical and oxidant species in the atmosphere, with a Cu cluster, a new generation atomic metal catalyst, is presented. The open-shell nature of the reactant species is properly accounted for by using the multireference perturbation theory, allowing the experimentally confirmed resistivity of Cu clusters toward oxidation to be investigated. Approximate reaction pathways for the transition from physisorption to chemisorption are calculated for the interaction of O with quasi-iso-energetic trapezoidal planar and trigonal bipyramidal structures.

Metal clusters synthesized in helium droplets: structure and dynamics from experiment and theory.

Metal clusters have drawn continuous interest because of their high potential for the assembly of matter with special properties that may significantly differ from the corresponding bulk. Controlled combination of particular elements in one nanoparticle can increase the options for the creation of new materials for photonic, catalytic, or electronic applications. Superfluid helium droplets provide confinement and ultralow temperature, i.

Thermally Induced Diffusion and Restructuring of Iron Triade (Fe, Co, Ni) Nanoparticles Passivated by Several Layers of Gold.

The temperature-induced structural changes of Fe-, Co-, and Ni-Au core-shell nanoparticles with diameters around 5 nm are studied via atomically resolved transmission electron microscopy. We observe structural transitions from local toward global energy minima induced by elevated temperatures. The experimental observations are accompanied by a computational modeling of all core-shell particles with either centralized or decentralized core positions.

Geometry optimization using Gaussian process regression in internal coordinate systems.

Locating the minimum energy structure of molecules, typically referred to as geometry optimization, is one of the first steps of any computational chemistry calculation. Earlier research was mostly dedicated to finding convenient sets of molecule-specific coordinates for a suitable representation of the potential energy surface, where a faster convergence toward the minimum structure can be achieved. More recent approaches, on the other hand, are based on various machine learning techniques and seem to revert to Cartesian coordinates instead for practical reasons.

Exploring the Catalytic Properties of Unsupported and TiO-Supported Cu Clusters: CO Decomposition to CO and CO Photoactivation.

In this work, we explore the decomposition of CO on unsupported and TiO-supported Cu clusters via computational modeling, using both finite cluster and periodic slab structures of the rutile TiO(110) surface. While the energy needed for C=O bond breaking is already significantly reduced upon adsorption onto the unsupported metal catalyst (it drops from 7.8 to 1.

Machine Learning in Computational Chemistry: An Evaluation of Method Performance for Nudged Elastic Band Calculations.

The localization of transition states and the calculation of reaction pathways are routine tasks of computational chemists but often very CPU-intense problems, in particular for large systems. The standard algorithm for this purpose is the nudged elastic band method, but it has become obvious that an "intelligent" selection of points to be evaluated on the potential energy surface can improve its convergence significantly. This article summarizes, compares, and extends known strategies that have been heavily inspired by the machine learning developments of recent years.

Synthesis of nanosized vanadium(v) oxide clusters below 10 nm.

Vanadium oxide clusters with a mean diameter below 10 nm are investigated by high resolution Scanning Transmission Electron Microscopy (STEM), Electron Energy Loss Spectroscopy (EELS) and UV-vis absorption spectroscopy. The clusters are synthesised by sublimation from bulk vanadium(v) oxide, in combination with a pick-up by superfluid helium droplets. The latter act as reaction chambers which enable cluster growth under fully inert and solvent-free conditions.

Effects of the Core Location on the Structural Stability of Ni-Au Core-Shell Nanoparticles.

Structural changes of Ni-Au core-shell nanoparticles with increasing temperature are studied at atomic resolution. The bimetallic clusters, synthesized in superfluid helium droplets, show a centralized Ni core, which is an intrinsic feature of the growth process inside helium. After deposition on SiN , the nanoparticles undergo a programmed temperature treatment in vacuum combined with an in situ transmission electron microscopy study of structural changes.

On the passivation of iron particles at the nanoscale.

The oxidation of Fe@Au core@shell clusters with sizes below 5 nm is studied high resolution scanning transmission electron microscopy. The bimetallic nanoparticles are grown in superfluid helium droplets under fully inert conditions, avoiding any effect of solvents or template structures, and deposited on amorphous carbon. Oxidation resistivity is tested by exposure to oxygen at ambient conditions.

Increasing the optical response of TiO and extending it into the visible region through surface activation with highly stable Cu clusters.

The decoration of semiconductors with subnanometer-sized clusters of metal atoms can have a strong impact on the optical properties of the support. The changes induced differ greatly from effects known for their well-studied, metallic counterparts in the nanometer range. In this work, we study the deposition of Cu clusters on a TiO surface and investigate their influence on the photon-absorption properties of TiO nanoparticles the computational modeling of a decorated rutile TiO (110) surface.

Vanadium(V) oxide clusters synthesized by sublimation from bulk under fully inert conditions.

Oxide nanoparticles in the size range of a few nanometers are typically synthesized in solution or laser ablation techniques, which open numerous channels for structural change chemical reactions or fragmentation processes. In this work, neutral vanadium oxide nanoparticles are instead synthesized by sublimation from bulk in combination with a pickup by superfluid helium droplets. Mass spectroscopy measurements clearly demonstrate the preservation of the bulk stoichiometric ratio of vanadium to oxygen in He-grown nanoparticles, indicating a tendency towards tetrahedral coordination of the vanadium centers in finite geometries.

Conservation of Hot Thermal Spin-Orbit Population of P Atoms in a Cold Quantum Fluid Environment.

The 0.4 K internal temperature of superfluid helium nanodroplets is believed to guarantee a corresponding ground-state population of dopant atoms and molecules inside this cryogenic matrix. We have recorded 6s ← 5p excitation spectra of indium atoms in helium droplets and found two absorption bands separated by about 2000 cm, a value close to the spin-orbit (SO) splitting of the In P ground state.