Nitrogen Reduction to Ammonia on a Fe16 Nanocluster: A Computational Study of Catalysis.

The sequence of elementary steps leading to reductive ammonia formation from N2 and H2 catalyzed by a Fe16 cluster is studied using generalized gradient approximation density functional theory and an all-electron basis set of triple-ζ quality. The computational methods are validated by comparison to experimental data such as binding energies where possible. First, the associative and dissociative attachment of N2 to Fe16 is considered, followed by exploration of the pathways leading to distal (Fe16-N-NH2) and enzymatic (NFe16-NH2) formation of an amino group. Next, the pathways leading to NH3 formation in both distal and enzymatic cases are examined. Two mechanisms for NH3 detachment have been discovered. An interesting peculiarity of the pathways is that they often proceed with total spin fluctuations, which are related to the rupture and formation of bonds on the surface of the catalyst over the course of the reactions. The reaction Fe16 + N2 + 2H2 → Fe16NH + NH3 is found to be exothermic by 1.02 eV (93.8 kJ/mol).

Mechanisms of Complete Dissociation of CO2 on Iron Clusters.

Dissociation of CO2 on iron clusters was studied by using semilocal density functional theory and basis sets of triple-zeta quality. Fe2 , Fe4 , and Fe16 clusters were selected as the representative host clusters. When searching for isomers of Fen CO2 , n=2, 4 and 16 corresponding to carbon dioxide attachment to the host clusters, its reduction to O and CO, and to the complete dissociation, it was found that the total spin magnetic moments of the lowest energy states of the isomers are often quenched with respect to those of initial reagents Fen +CO2 . Dissociation pathways of the Fe2 +CO2 , Fe4 +CO2 , and Fe16 +CO2 reactions contain several transition states separated by the local minima states; therefore, a natural question is where do the spin flips occur? Since lifetimes of magnetically excited states were shown to be of the order of 100 fs, the search for the CO2 dissociation pathways was performed under the assumption that magnetic deexcitation may occur at the intermediate local minima. Two dissociation pathways were obtained for each Fen +CO2 reaction using the gradient-based methods. It was found that the Fe2 +CO2 reaction is endothermic with respect to both reduction and complete dissociation of CO2 , whereas the Fe4 +CO2 and Fe16 +CO2 reactions are exothermic to both reduction and complete dissociation of carbon dioxide. The CO2 reduction was found to be more favorable than its complete dissociation in the Fe4 case.

Structure and Chemical Bonding in Medium-Size Boron Clusters Doped with Praseodymium.

After reports of unusually low oxidation states of lanthanide elements in Ln-B clusters and their inverse sandwich geometrical topologies, the interest shifted from boride clusters doped with transition metal (TM) elements to the boride clusters doped with lanthanide atoms. In this work, the results obtained by a combined approach consisting of CALYPSO structure predictions and density functional theory (DFT) calculations for the neutral and anionic PrBn series, n = 7-16, are reported. A close agreement between our calculated vertical detachment energies and experimental data supports the accuracy of the results obtained. Contrary to the medium-size TM-doped medium boron clusters, which prefer three types of structural configurations, all lowest-energy states of the medium-size Pr-doped boron clusters have half-sandwich geometries. An interesting structural evolution pattern was found for both neutral and anionic PrBn clusters at n = 7, 10, 13, and 16, which includes quasi-planar B7 units half-sandwiching the Pr atom. Unusual oxidation numbers of +2 and +1 were found for the Pr atom in the PrB7- and PrB8- anions, respectively. Chemical bonding analysis for the neutral PrB7 and PrB13 clusters revealed that their high stability stems from interactions between Pr 5d and B 2p orbitals. A stable tubular-shaped PrB30 cluster is proposed as a promising building block for boron-based nanotubes.

Coulomb Explosion Dynamics of Multiply Charged para-Nitrotoluene Cations.

This work explores Coulomb explosion (CE) dissociation pathways in multiply charged cations of para-nitrotoluene (PNT), a model compound for nitroaromatic energetic molecules. Experiments using strong-field ionization and mass spectrometry indicate that metastable cations PNT2+ and PNT3+ undergo CE to produce NO2+ and NO+. The experimentally measured kinetic energy release from CE upon formation of NO2+ and NO+ agrees qualitatively with the kinetic energy release predicted by computations of the reaction pathways in PNT2+ and PNT3+ using density functional theory (DFT). Both DFT computations and mass spectrometry identified additional products from CE of highly charged PNTq+ cations with q > 3. The dynamical timescales required for direct CE of PNT2+ and PNT3+ to produce NO2+ were estimated to be 200 and 90 fs, respectively, using ultrafast disruptive probing measurements.

Ultrafast Dynamics of Nitro-Nitrite Rearrangement and Dissociation in Nitromethane Cation.

We report new insights into the ultrafast rearrangement and dissociation dynamics of nitromethane cation (NM+) using pump-probe measurements, electronic structure calculations, and ab initio molecular dynamics simulations. The "roaming" nitro-nitrite rearrangement (NNR) pathway involving large-amplitude atomic motion, which has been previously described for neutral nitromethane, is demonstrated for NM+. Excess energy resulting from initial population of the electronically excited D2 state of NM+ upon strong-field ionization provides the necessary energy to initiate NNR and subsequent dissociation into NO+. Both pump-probe measurements and molecular dynamics simulations are consistent with the completion of NNR within 500 fs of ionization with dissociation into NO+ and OCH3 occurring ∼30 fs later. Pump-probe measurements indicate that NO+ formation is in competition with the direct dissociation of NM+ to CH3+ and NO2. Electronic structure calculations indicate that a strong D0 → D1 transition can be excited at 650 nm when the C-N bond is stretched from its equilibrium value (1.48 Å) to 1.88 Å. On the other hand, relaxation of the NM+ cation after ionization into D0 occurs in less than 50 fs and results in observation of intact NM+. Direct dissociation of the equilibrium NM+ to produce NO2+ and CH3 can be induced with 650 nm excitation via a weakly allowed D0 → D2 transition.

Features and Consequences of Isopropanol Burning off PTFE-rGO Aerogels.

An improved procedure for the preparation of aerogel granules of polytetrafluoroethylene-graphene oxide (PTFE-GO) with a composition of 50:50 (in wt %) and a specific density of 35 ± 2 mg/cm3 is described. The technique practically excludes the granule cracking. The specific density of the pellets after reduction using hydrazine vapor and annealing at 370 °C decreased to 29 ± 2 mg/cm3. The PTFE-reduced GO (rGO) pellets obtained were tested as a recyclable sorbent for isopropyl alcohol (IPA) in sorption/combustion cycles. It has been shown that the aerogel sorption capacity for IPA increases from 35.6 to 39.3 g/g as a result of alcohol burning off. During the combustion of IPA, the temperature of an individual pellet can exceed 300 °C. When several contingent pellets are burned, the temperature of their heating increases. The fine-pored structure of the near-surface layer of the granule is destroyed during the alcohol burning, the internal structure with larger pores is exposed, and the relative proportion of PTFE on the surface of the granules decreases. It was also shown that the specific surface area of PTFE-rGO increases from 26 to 49 m2/g during cycling.

Dissociation of dinitrogen on iron clusters: a detailed study of the Fe16 + N2 case.

The coalescence of two Fe8N as well as the structure of the Fe16N2 cluster were studied using density functional theory with the generalized gradient approximation and a basis set of triple-zeta quality. It was found that the coalescence may proceed without an energy barrier and that the geometrical structures of the resulting clusters depend strongly on the mutual orientations of the initial moieties. The dissociation of N2 is energetically favorable on Fe16, and the nitrogen atoms share the same Fe atom in the lowest energy state of the Fe16N2 species. The attachment of two nitrogen atoms leads to a decrease in the total spin magnetic moment of the ground-state Fe16 host by 6 µB due to the peculiarities of chemical bonding in the magnetic clusters. In order to gain insight into the dependence of properties on charge and to estimate the bonding energies of both N atoms, we performed optimizations of Fe16N and the singly charged ions of both Fe16N2 and Fe16N. It was found that the electronic properties of the Fe16N2 cluster, such as electron affinity and ionization energy, do not appreciably depend on the attachment of nitrogen atoms but that the average binding energy per atom changes significantly. The lowering in total energy due to the attachment of two N atoms was found to be nearly independent of charge. The IR and Raman spectra were simulated for Fe16N2 and its ions, and it was found that the positions of the most intense peaks in the IR spectra strongly depend on charge and therefore present fingerprints of the charged states. The chemical bonding in the ground-state Fe16N20,±1 species was described in terms of the localized molecular orbitals.

Superhalogens Among 3d-Metal Compounds: MF4, MF6, MF12, and MF18 (M = Sc-Zn).

The ground states of the neutral and anionic tetrafluoride and hexafluoride series of 3d-metal atoms from Sc to Zn were assigned by using a double-check approach in which the pure and hybrid density functional methods were interchangeably used. It was confirmed that all these neutral fluorides are superhalogens except for TiF4. The electron affinities of the hexafluorides were shown to be consistently higher than those of the tetrafluorides in accordance with the superhalogen conception of the extra electron delocalization over a larger number of the electronegative ligands. In the search for mononuclear fluorides possessing higher electron affinities, we considered the M(F2)6- and M(F3)6- series where M = Sc-Zn. We found that the optimized geometrical structures in both series may be described as MF6-- k(F2), k = 3 and 6, of which the geometry of the MF6- core mimics that of the corresponding hexafluoride anion and the F2 dimers are kept in a bound state by polarizing forces. In these cases, the electron affinity is decreased by tenths of eV with respect to the electron affinity of the core hexafluorides due to a confinement of the extra electron by the F2 environment.

Evolution of Ferromagnetic and Antiferromagnetic States in Iron Nitride Clusters FenN and FenN2 (n = 1-10).

First-principles density functional theory calculations on neutral and singly negatively and positively charged iron clusters Fen and iron nitride clusters FenN and FenN2 (n = 1-10) in the range of 1 ≤ n ≤ 10 revealed that there is a strong competition between ferromagnetic and antiferromagnetic states especially in the FenN20,±1 cluster series. This phenomenon was related to superexchange via a bridging N atom between two iron atoms in the FenN20,±1 cluster series and to a double superexchange effect via a Fe atom shared by two N atoms in the FenN20,±1 series. A thorough examination of the structure-energy-spin state relationships in these clusters is conducted, leading to new insights and confirmation of available experimental results on structural parameters and dissociation energetics. The bond energies of both nitrogen atoms in the FenN2 series are approximately the same. They weakly depend on the charge of the host cluster and fluctuate around 5.5 eV when moving along the series. The energy of N2 desorption is relatively small; it varies by about 1.0 eV and depends on the charge of the cluster. The experimental finding that N2 dissociates on the Fen+ clusters beginning with n = 4 was supported by the results of our computations. Our computed values of the Fen+-N bonding energies agree with the experimental data within the experimental uncertainty bars. It was found that the attachment of one or two N atoms does not seriously affect the polarizability, electron affinity, or ionization energy of the host iron clusters independent of the charge.

Dissociation of Singly and Multiply Charged Nitromethane Cations: Femtosecond Laser Mass Spectrometry and Theoretical Modeling.

Dissociation pathways of singly- and multiply charged gas-phase nitromethane cations were investigated with strong-field laser photoionization mass spectrometry and density functional theory computations. There are multiple isomers of the singly charged nitromethane radical cation, several of which can be accessed by rearrangement of the parent CH3-NO2 structure with low energy barriers. While direct cleavage of the C-N bond from the parent nitromethane cation produces NO2+ and CH3+, rearrangement prior to dissociation accounts for fragmentation products including NO+, CH2OH+, and CH2NO+. Extensive Coulomb explosion in fragment ions observed at high laser intensity indicates that rapid dissociation of multiply charged nitromethane cations produces additional species such as CH2+, H+, and NO22+.  On the basis of analysis of Coulomb explosion in the mass spectral signals and pathway calculations, sufficiently intense laser fields can remove four or more electrons from nitromethane.

NbB12-: a new member of half-sandwich type doped boron clusters with high stability.

A theoretical study of geometrical structures and electronic properties of niobium-doped boron clusters is performed using the CALYPSO approach for the global minimum search followed by density functional theory calculations. It is found that the global minima obtained for the neutral clusters correspond to the half-sandwich structures at n = 10-17 and the tubular-type structures at n = 18-20. The geometrical patterns in the anion series are more complex. The geometries undergo a transformation from the wheel-like structure of NbB10- to the half-sandwich ones beginning at n = 11 and finally to the drum-shaped structures at n ≥ 18. A fascinating NbB12- cluster is uncovered by our structural search, which shows robust stability and can be considered as a new member of the half-sandwich transition metal doped boron clusters. The chemical bond analysis indicates that the high stability is due to the strong interactions between the Nb atom and the B12 host as well as to the strong B-B covalent bonds. Our study will enrich the database of geometrical structures of transition metal doped boron clusters and will stimulate future synthesis of boron-based nanomaterials.

Homocoupling and Heterocoupling of Grignard Perfluorobenzene Reagents via Aryne Intermediates: A DFT Study.

Perfluorobenzenes are reactive species with the lowest magnesium metalation barriers among all hexahalobenzenes. This fact makes them good candidates for the study of heterocoupling reactions of the Grignard type. In this work, we investigated a number of pathways for both heterocoupling and homocoupling reactions and estimated the solvated energy barrier heights. According to the results of our density functional theory (DFT)-based computations, the heterocoupling reaction (C6F5)MgF + C6F6 is a single-step process. We have also studied the (C6F5)MgF + (C6F5)MgF homocoupling reaction with an aryne intermediate. In this particular reaction, a carbon-carbon bond is formed between two nucleophilic carbon centers in a chemically predictable way. The final product, (C12F9)Mg2F3, retains even stronger nucleophilic activity than that of the starting (C6F5)MgF reagent. A very surprising result of our calculations is that this homocoupling of two nucleophilic centers is spontaneous in THF solvent.

Ultrafast coherent vibrational dynamics in dimethyl methylphosphonate radical cation.

Femtosecond pump-probe measurements of the nerve agent simulant dimethyl methylphosphonate (DMMP) demonstrate the preparation of a robust coherent vibrational state in the corresponding radical cation. The oscillations in the transient ion yields have a period of 45 fs (750 cm-1), which is at least 3 times faster than any previously observed oscillations in polyatomic radical cations. Use of 1200-1600 nm, as opposed to 800 nm, wavelengths for ionization increases the oscillation amplitude by a factor of 5 and doubles the number of visible oscillation periods from 6 to 12, indicating that an adiabatic ionization mechanism significantly enhances preparation of the coherent state. The coherent motion is assigned to a bending mode in DMMP+ with frequency in the range of 742.2-754.7 cm-1 based on the results of DFT calculations. The observation of coherent nuclear dynamics in the dissociation of DMMP+ suggests the potential utility of coherent control schemes for controlling the dissociation of DMMP and related molecules, which has important implications for developing detection and decontamination technologies for organophosphorus chemical warfare agents.

Insights into the effects produced by doping of medium-sized boron clusters with ruthenium.

Modification of properties of boron nanoparticles by doping with transition metals presents a challenging problem because the number of isomers of both doped and un-doped nanoparticles rapidly increases with the nanoparticle size. Here, we perform a study of neutral and anionic Ru-doped boron clusters RuBn (n = 9-20) using the unbiased CALYPSO structural search method in combination with density functional theory calculations. Our results show that the neutral RuB9 cluster possesses a perfect planar wheel-like geometrical structure, whereas the RuBn clusters prefer structures of the half-sandwich type in the range of 10 ≤ n ≤ 14, drum-like type in the range of 15 ≤ n ≤ 18 and cage-like structures for larger n values. The geometrical structures of the lowest total energy states of the RuBn- anions are similar to those of the corresponding neutrals, except for RuB10-, RuB11-, RuB14-, RuB15- and RuB20-. The neutral RuB12 and RuB14 clusters are found to exhibit enhanced stability with respect to the rest of the RuBn clusters due to the delocalized bonding between the Ru atom and the boron host.

Dissociation dynamics of 3- and 4-nitrotoluene radical cations: Coherently driven C-NO2 bond homolysis.

Monosubstituted nitrotoluenes serve as important model compounds for nitroaromatic energetic molecules such as trinitrotoluene. This work investigates the ultrafast nuclear dynamics of 3- and 4-nitrotoluene radical cations using femtosecond pump-probe measurements and the results of density functional theory calculations. Strong-field adiabatic ionization of 3- and 4-nitrotoluene using 1500 nm, 18 fs pulses produces radical cations in the ground electronic state with distinct coherent vibrational excitations. In both nitrotoluene isomers, a one-photon excitation with the probe pulse results in NO2 loss to form C7H7+, which exhibits out-of-phase oscillations in yield with the parent molecular ion. The oscillations in 4-nitrotoluene with a period of 470 fs are attributed to the torsional motion of the NO2 group based on theoretical results showing that the dominant relaxation pathway in 4-nitrotoluene radical cations involves the rotation of the NO2 group away from the planar geometry. The distinctly faster oscillation period of 216 fs in 3-nitrotoluene is attributed to an in-plane bending motion of the NO2 and CH3 moieties based on analysis of the normal modes. These results demonstrate that coherent nuclear motions determine the probability of C-NO2 homolysis in the nitrotoluene radical cations upon optical excitation within several hundred femtoseconds of the initial ionization event.

Structure and Electronic Properties of Neutral and Negatively Charged RhBn Clusters (n = 3-10): A Density Functional Theory Study.

The geometrical structure and electronic properties of the neutral RhBn and singly negatively charged RhBn- clusters are obtained in the range of 3 ≤ n ≤ 10 using the unbiased CALYPSO structure search method and density functional theory (DFT). A combination of the PBE0 functional and the def2-TZVP basis set is used for determining global minima on potential energy surfaces of the Rh-doped Bn clusters. The photoelectron spectra of the anions are simulated using the time-dependent density functional theory (TD-DFT) method. Good agreement between our simulated and experimentally obtained photoelectron spectra for RhB9- provides support to the validity of our theoretical method. The relative stabilities of the ground-state RhBn and RhBn- clusters are estimated using the calculated binding energies, second-order total energy differences, and HOMO-LUMO gaps. It is found that RhB7 and RhB8- are the most stable species in the neutral and anionic series, respectively. The chemical bonding analysis reveals that the RhB8-cluster possesses two sets of delocalized σ and π bonds. In both cases, the Hückel 4N + 2 rule is fulfilled and this cluster possesses both σ and π aromaticities.

Structure and properties of iron oxide clusters: From Fe6 to Fe6 O20 and from Fe7 to Fe7 O24.

Geometrical and electronic structures of the neutral and singly negatively charged Fe6 On and Fe7 Om clusters in the range of 1 ≤ n ≤ 20 and 1 ≤ m ≤ 24, respectively, are computed using density functional theory with the generalized gradient approximation. The largest clusters in the two series, Fe6 O20 and Fe7 O24 , can be described as Fe(FeO4 )5 and Fe(FeO4 )6 or alternatively as [FeO5 ](FeO3 )5 and [FeO6 ](FeO3 )6 , respectively. The Fe6 O20 and Fe7 O24 clusters possess adiabatic electron affinities (EAad ) of 5.64 eV and 5.80 eV and can be attributed to the class of hyperhalogens since FeO4 is an unique closed-shell superhalogen with the EAad of 3.9 eV. The spin character of the lowest total energy states in both series changes from ferromagnetic to ferrimagnetic or antiferromagnetic when the first FeOFe bridge is formed. Oxidation decreases substantially the polarizability per atom of the initial bare clusters; namely, from 5.98 Å(3) of Fe6 to 2.47 Å(3) of Fe6 O20 and from 5.67 Å(3) of Fe7 to 2.38 Å(3) of Fe7 O24 . The results of our computations pertaining to the binding energies of O, Fe, O2 , and FeO in the Fe7 Om series provide an explanation for the experimentally observed abundance of the iron oxide nanoparticles with stoichiometric compositions. © 2016 Wiley Periodicals, Inc.

Hydrophobization of Reduced Graphene Oxide Aerogel Using Soy Wax to Improve Sorption Properties.

A special technique has been developed for producing a composite aerogel which consists of graphene oxide and soy wax (GO/wax). The reduction of graphene oxide was carried out by the stepwise heating of this aerogel to 250 °C. The aerogel obtained in the process of the stepwise thermal treatment of rGO/wax was studied by IR and Raman spectroscopy, scanning electron microscopy, and thermogravimetry. The heat treatment led to an increase in the wax fraction accompanied by an increase in the contact angle of the rGO/wax aerogel surface from 136.2 °C to 142.4 °C. The SEM analysis has shown that the spatial structure of the aerogel was formed by sheets of graphene oxide, while the wax formed rather large (200-1000 nm) clumps in the folds of graphene oxide sheets and small (several nm) deposits on the flat surface of the sheets. The sorption properties of the rGO/wax aerogel were studied with respect to eight solvent, oil, and petroleum products, and it was found that dichlorobenzene (85.8 g/g) and hexane (41.9 g/g) had the maximum and minimum sorption capacities, respectively. In the case of oil and petroleum products, the indicators were in the range of 52-63 g/g. The rGO/wax aerogel was found to be highly resistant to sorption-desorption cycles. The cyclic tests also revealed a swelling effect that occurred differently for different parts of the aerogel.

Geometric and electronic diversity of metal doped boron clusters.

Being intermediate between small compounds and bulk materials, nanoparticles possess unique properties different from those of atoms, molecules, and bulk matter. In the past two decades, a combination of cluster structure prediction algorithms and experimental spectroscopy techniques was successfully used for exploration of the ground-state structures of pure and metal-doped boron clusters. The fruitfulness of this dual approach is well illustrated by the discovery of intriguing microstructures and unique physicochemical properties such as aromaticity and bond fluxionality for both boron and metal-doped boron clusters. Our review starts with an overview of geometrical configurations of pure boron clusters Bn, which are presented by planar, nanotube, bilayer, fullerene-like and core-shell structures, in a wide range ofnvalues. We consider next recent advances in studies of boron clusters doped with metal atoms paying close and thoughtful attention to modifications of geometric and electronic structures of pure boron clusters by heteroatoms. Finally, we discuss the possibility of constructing boron-based nanomaterials with specific functions from metal-boron clusters. Despite a variety of fruitful results obtained in numerous studies of boron clusters, the exploration of boron-based chemistry has not yet reached its peak. The intensive research continues in this area, and it should be expected that it brings exciting discoveries of intriguing new structures.