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. We investigate the optical stimulation of vibrationally induced molecular magnetism and estimate changes in the magnetic shielding constants for confirmation by future experiments.

Stability and Reversible Oxidation of Sub-Nanometric Cu5 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 Cu5 clusters are resistant to irreversible oxidation at least up to 773 K, even in the presence of 0.15 mbar of oxygen. These experimental findings can be formally described by a theoretical model which combines dispersion-corrected DFT and first principles thermochemistry revealing that most of the adsorbed O2 molecules are transformed into superoxo and peroxo species by an interplay of collective charge transfer within the network of Cu atoms and large amplitude "breathing" motions. A chemical phase diagram for Cu oxidation states of the Cu5 -oxygen system is presented, clearly different from the already known bulk and nano-structured chemistry of Cu.

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 V2O5 nanoparticles can be generated by sublimation from the bulk and deposited without affecting their original stoichiometry. Interestingly, our follow-up attempts to create Au@V2O5 core@shell particles do not yield the expected encapsulated structure. Instead, Janus particles of Au and V2O5 with diameters between 10 and 20 nm are identified after deposition. At the interface of the Au and the V2O5 parts we observe an epitaxial-like growth of the vanadium oxide next to the Au structure. To test the temperature stability of these Janus-type particles, the samples are heated in situ during the STEM measurements from room temperature up to 650 °C, where a reduction from V2O5 to V2O3 is followed by a restructuring of the gold atoms to form a Wulff-shaped cluster layer. The temperature dependent dynamic interplay between gold and vanadium oxide in structures of only a few nanometer size is the central topic of this contribution to the Faraday Discussion.

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. The performance of the algorithm is tested for a selection of gas sieving scenarios on porous, N-functionalized graphene and for the intermolecular interaction of CH4 and N2.

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.g., realized through electromagnetic fields or molecular encapsulation. We illustrate this on the example of fullerene-encapsulated nitric oxide, and provide a prediction of its interesting, perturbed vibronic spectrum.

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.e. an ideal environment for the atom-by-atom aggregation of a new nanoparticle. This perspective presents a review of the current research progress on the synthesis of tailored metal and metal oxide clusters including core-shell designs, their characterization within the helium droplet beam, deposition on various solid substrates, and analysis via surface diagnostics. Special attention is given to the thermal properties of mixed metal clusters and questions about alloy formation on the nanoscale. Experimental results are accompanied by theoretical approaches employing computational chemistry, molecular dynamics simulations and He density functional theory.

Nonadiabatic Effects in the Molecular Oxidation of Subnanometric Cu5 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, Cu5 clusters have proven to be exceptionally resistant to irreversible oxidation, i.e., the dissociative chemisorption of molecular oxygen. Besides providing reasons for this behavior in the case of heavy loading with molecular oxygen, we investigate the competition between physisorption and molecular chemisorption from the perspective of nonadiabatic effects. Landau-Zener theory is applied to the Cu5(O2)3 complex to estimate the probability for a switching between the electronic states correlating the neutral O2 + Cu5(O2)2 and the ionic O2- + (Cu5(O2)2)+ fragments in a diabatic representation. Our work demonstrates the involvement of strong nonadiabatic effects in the associated charge transfer process, which might be a common motive in reactions involving subnanometric metal structures.

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., J. Chem. Phys.2016, 145, 181101), this spatially quenched reaction was characterized as a harpoon-type or long-range electron transfer in a previous high-level ab initio study (de Lara-Castells et al., J. Phys. Chem. Lett.2017, 8, 4284). To go beyond the static approach, classical and quantum PIMD simulations are performed at 2 K, slightly below the critical temperature for helium superfluidity (2.172 K). Calculations are executed in the NVT ensemble as well as the NVE ensemble to provide insights into real-time dynamics. A droplet size of 2090 atoms is assumed to study the impact of spatial hindrance on reactivity. By changing the number of beads in the PIMD simulations, the impact of quantization can be studied in greater detail and without an implicit assumption of superfluidity. We find that the reaction probability increases with higher levels of quantization. Our findings confirm earlier, static predictions of a rotational motion of the Cs2 dimer upon reacting with the fullerene, involving a substantial displacement of helium. However, it also raises the new question of whether the interacting species are driven out-of-equilibrium after impurity uptake, since reactivity is strongly quenched if a full thermal equilibration is assumed. More generally, our work points towards a novel mechanism for long-range electron transfer through an interplay between nuclear quantum delocalization within the confining medium and delocalized electronic dispersion forces acting on the two reactants.

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. We show that the combination of Gaussian process regression with those coordinate systems employed by state-of-the-art geometry optimizers can significantly improve the performance of this powerful machine learning technique. This is demonstrated on a benchmark set of 30 small covalently bonded molecules.

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. High-resolution STEM images of deposited vanadium oxide particles allowing for the determination of lattice constants, clearly indicate a dominating presence of V2O5. This finding is further supported by UV-vis absorption spectra of nanoparticles after deposition on fused silica substrates, which indicates that the oxidation state of the material is preserved over the entire process. From the results of the UV-vis measurement, the band gap of the nanosized V2O5 could be determined to be 3.3 eV. The synthesis approach provides a route to clean V2O5 clusters as it does not involve any surfactant or solvents, which is crucial for an unbiased measurement of intrinsic catalyst properties.

Conservation of Hot Thermal Spin-Orbit Population of 2P 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-1, a value close to the spin-orbit (SO) splitting of the In 2P ground state. The intensities of the bands agree with a thermal population of the 2P1/2 and 2P3/2 states at 870 K, the temperature of the In pick-up cell. Applying femtosecond pump-probe spectroscopy, we found the same dynamical response of the helium solvation shell after the photoexcitation of the two bands. He-density functional theory simulations of the excitation spectra are in agreement with the bimodal structure. Our findings show that the population of SO levels of hot dopants is conserved after pick-up inside the superfluid droplet. Implications for the interpretation of experiments on molecular aggregates are discussed.

Chiral Separation via Molecular Sieving: A Computational Screening of Suitable Functionalizations for Nanoporous Graphene.

In a recent study [Angew. Chem. Int. Ed., 2014, 53, 9957-9960] a new concept of chiral separation has been suggested, which is based on functionalized, nanoporous sheets of graphene. In this follow-up article we discuss the underlying principle in greater detail and make suggestions for suitable pore functionalizations with respect to a selection of chiral prototype molecules. Considering drug molecules as future targets for a chiral separation via membranes, the necessary pore sizes represent a big challenge for standard methods of computational chemistry. Therefore, we test two common force fields (GAFF, CGenFF) as well as a semiempirical tight-binding approach recently developed by the Grimme group (GFN-xTB) against the computationally much more expensive density functional theory. We identify the GFN-xTB method as the most suitable approach for future simulations of functionalized pores for the given purpose, as it is able to produce reaction pathways in very good agreement with density functional theory, even in cases where force fields tend to an extreme overestimation of barrier heights.

Spatial quenching of a molecular charge-transfer process in a quantum fluid: the Csx-C60 reaction in superfluid helium nanodroplets.

A recent experimental study [Renzler et al., J. Chem. Phys., 2016, 145, 181101] on superfluid helium nanodroplets reported different reactivities for Cs atoms and Cs2 dimers with C60 fullerenes inside helium droplets. Alkali metal atoms and clusters are heliophobic, therefore typically residing on the droplet surface, while fullerenes are fully immersed into the droplet. In this theoretical study, which combines standard methods of computational chemistry with orbital-free helium density functional theory, we show that the experimental findings can be interpreted in the light of a quenched electron-transfer reaction between the fullerene and the alkali dopant, which is additionally hindered by a reaction barrier stemming from the necessary extrusion of helium upon approach of the two reactants.

Rydberg states of alkali atoms on superfluid helium nanodroplets: inside or outside?

Electronic excitations of an electron bound to an alkali metal ion inside a droplet of superfluid 4He are computed via a combination of helium density functional theory and the numerical integration of the Schrödinger equation for a single electron in a modified, He density dependent atomic pseudopotential. The application of a spectral method to the radial part of the valence electron wavefunction allows the computation of highly excited Rydberg states. For low principal quantum numbers, the energy required to push the electron outward is larger than the solvation energy of the ion. However, for higher principal quantum numbers the situation is reversed, which suggests the stability of a system where the ion sits inside the droplet while the valence electron orbits the nanodroplet.

Thermally induced breakup of metallic nanowires: experiment and theory.

We present time-resolved transmission electron microscopy studies of the degradation of Au, Ag, Cu and Ni nanowires deposited on a heated support. The wires are grown under fully inert conditions in superfluid helium droplets and deposited onto amorphous carbon. The inherent stability of these pristine metal nanowires with diameters below 10 nm is investigated in the absence of any stabilizers, templates or solvents. The phenomenon of Rayleigh-breakup, a consequence of diffusion processes along the wire surfaces, is analysed in situ via scans over time and support temperature. Our experimental efforts are combined with simulations based on a novel model featuring a cellular automaton to emulate surface diffusion. Based on this model, correlations between the material parameters and actual breakup behaviour are studied.

Quantum confinement of molecular deuterium clusters in carbon nanotubes: ab initio evidence for hexagonal close packing.

An ab initio study of quantum confinement of deuterium clusters in carbon nanotubes is presented. First, density functional theory (DFT)-based symmetry-adapted perturbation theory is used to derive parameters for a pairwise potential model describing the adsorbate-nanotube interaction. Next, we analyze the quantum nuclear motion of N D2 molecules (N < 4) confined in carbon nanotubes using a highly accurate adsorbate-wave-function-based approach, and compare it with the motion of molecular hydrogen. We further apply an embedding approach and study zero-point energy effects on larger hexagonal and heptagonal structures of 7-8 D2 molecules. Our results show a preference for crystalline hexagonal close packing hcp of D2 molecules inside carbon nanotubes even at the cost of a reduced volumetric density within the cylindrical confinement.

Electric dipole moments and chemical bonding of diatomic alkali-alkaline earth molecules.

We investigate the properties of alkali-alkaline earth diatomic molecules in the lowest Σ(+) states of the doublet and quartet multiplicity by ab initio calculations. In all sixteen cases studied, the permanent electric dipole moment points in opposite directions for the two spin states. This peculiarity can be explained by molecular orbital theory. We further discuss dissociation energies and bond distances. We analyze trends and provide an empirically motivated model for the prediction of the permanent electric dipole moment for combinations of alkali and alkaline earth atoms not studied in this work.

A systematic study on Pt based, subnanometer-sized alloy cluster catalysts for alkane dehydrogenation: effects of intermetallic interaction.

Platinum-based bimetallic nanoparticles are analyzed by the application of density functional theory to a series of tetrahedral Pt3X cluster models, with element X taken from the P-block, preferably group 14, or from the D-block around group 10. Almost identical cluster geometries allow a systematic investigation of electronic effects induced by different elements X. Choosing the propane-to-propene conversion as the desired dehydrogenation reaction, we provide estimates for the activity and selectivity of the various catalysts based on transition state theory. No significant Brønsted-Evans-Polanyi-relation could be found for the given reaction. A new descriptor, derived from an energy decomposition analysis, captures the effect of element X on the rate-determining step of the first hydrogen abstraction. Higher activities than obtained for pure Pt4 clusters are predicted for Pt alloys containing Ir, Sn, Ge and Si, with Pt3Ir showing particularly high selectivity.

The impact of doping rates on the morphologies of silver and gold nanowires grown in helium nanodroplets.

Silver and gold nanowires are grown within superfluid helium nanodroplets and investigated by high resolution electron microscopy after surface deposition. The wire morphologies depend on the rate of metal atom doping in the pickup sequence. While high doping rates result in a polycrystalline face-centered cubic nanowire structure, at lower doping rates the initial fivefold-symmetry seems to be preserved. An explanation for this observation is given by computer simulations, which allow the derivation of timescales for the nanowire growth process inside helium nanodroplets.