Exploring possible reaction pathways for the o‐atom transfer reactions to unsaturated substrates catalyzed by a [Ni‐NO2] ↔ [Ni‐NO] redox couple using DFT methods

The (nitro)(N‐methyldithiocarbamato)(trimethylphospane)nickel(II), [Ni(NO₂)(S₂CNHMe)(PMe₃)] complex catalyses efficiently the O‐atom transfer reactions to CO and acetylene. Energetically feasible sequence of elementary steps involved in the catalytic cycle of the air oxidation of CO and acetylene are proposed promoted by the Ni(NO₂)(S₂CNHMe)(PMe₃)] ↔ Ni(NO₂)(S₂CNHMe)(PMe₃) redox couple using DFT methods both in vacuum and dichloromethane solutions. The catalytic air oxidation of HC≡CH involves formation of a five‐member metallacycle intermediate, via a [3 + 2] cyclo‐addition reaction of HC≡CH to the Ni‐N = O moiety of the Ni(NO₂)(S₂CNHMe)(PMe₃)] complex, followed by a β H‐atom migration toward the C_α carbon atom of the coordinated acetylene and release of the oxidation product (ketene). The geometric and energetic reaction profile for the reversible [Ni( ‐NO₂)(S₂CNHMe)(PMe₃)] [Ni( ‐ONO)(S₂CNHMe)(PMe₃)] linkage isomerization has also been modeled by DFT calculations. © 2017 Wiley Periodicals, Inc.     

A Comparative Study of CO Oxidation on Nitrogen‐ and Phosphorus‐Doped Graphene

The geometry, electronic structure, and catalytic properties of nitrogen‐ and phosphorus‐doped graphene (N‐/P‐graphene) are investigated by density functional theory calculations. The reaction between adsorbed O₂ and CO molecules on N‐ and P‐graphene is comparably studied via Langmuir–Hinshelwood (LH) and Eley–Rideal (ER) mechanisms. The results indicate that a two‐step process can occur, namely, CO+O₂→CO₂+O_ads and CO+O_ads→CO₂. The calculated energy barriers of the first step are 15.8 and 12.4 kcal mol^?1 for N‐ and P‐graphene, respectively. The second step of the oxidation reaction on N‐graphene proceeds with an energy barrier of about 4 kcal mol^?1. It is noteworthy that this reaction step was not observed on P‐graphene because of the strong binding of O_ads species on the P atoms. Thus, it can be concluded that low‐cost N‐graphene can be used as a promising green catalyst for low‐temperature CO oxidation.     

Bent Carbon Surface Moieties as Active Sites on Carbon Catalysts for Phosgene Synthesis

Active sites in carbon‐catalyzed phosgene synthesis from gaseous CO and Cl₂ have been identified using C₆₀ fullerene as a model catalyst. The carbon atoms distorted from sp² coordination in non‐planar carbon units are concluded to generate active Cl₂. Experiments and density functional theory calculations indicate the formation of a surface‐bound [C₆₀???Cl₂] chlorine species with radical character as key intermediate during phosgene formation. It reacts rapidly with physisorbed CO in a two‐step Eley–Rideal‐type mechanism.     

Ordered Porous Nitrogen‐Doped Carbon Matrix with Atomically Dispersed Cobalt Sites as an Efficient Catalyst for Dehydrogenation and Transfer Hydrogenation of N‐Heterocycles

Single‐atom catalysts (SACs) have been explored widely as potential substitutes for homogeneous catalysts. Isolated cobalt single‐atom sites were stabilized on an ordered porous nitrogen‐doped carbon matrix (ISAS‐Co/OPNC). ISAS‐Co/OPNC is a highly efficient catalyst for acceptorless dehydrogenation of N‐heterocycles to release H₂. ISAS‐Co/OPNC also exhibits excellent catalytic activity for the reverse transfer hydrogenation (or hydrogenation) of N‐heterocycles to store H₂, using formic acid or external hydrogen as a hydrogen source. The catalytic performance of ISAS‐Co/OPNC in both reactions surpasses previously reported homogeneous and heterogeneous precious‐metal catalysts. The reaction mechanisms are systematically investigated using first‐principles calculations and it is suggested that the Eley–Rideal mechanism is dominant.     

Development of spin‐orbit coupling for stochastic configuration interaction techniques

To perform spin‐orbit coupling calculations on atoms and molecules, good zeroth‐order wavefunctions are necessary. Here, we present the software development of the Monte Carlo Configuration Interaction (MCCI) method, to enable calculation of such properties, where MCCI iteratively constructs a multireference wavefunction using a stochastic procedure. In this initial work, we aim to establish the efficacy of this technique in predicting the splitting of otherwise degenerate energy levels on a range of atoms and small diatomic molecules. It is hoped that this work will subsequently act as a gateway toward using this method to investigate singlet‐triplet interactions in larger multireference molecules. We show that MCCI can generate very good results using highly compact wavefunctions compared to other techniques, with no prior knowledge of important orbitals. Higher‐order relativistic effects are neglected and spin‐orbit coupling effects are incorporated using first‐order degenerate perturbation theory with the Breit‐Pauli Hamiltonian and effective nuclear charges in the one‐electron operator. Results are obtained and presented for B, C, O, F, Si, S, and Cl atoms and OH, CN, NO, and C₂ diatomic radicals including spin‐orbit coupling constants and the relative splitting of the lowest energy degenerate state for each species. Convergence of MCCI to the full configuration interaction result is demonstrated on the multireference problem of stretched OH. We also present results from the singlet‐triplet interaction between the and both the and states of the O₂ molecule. © 2017 Wiley Periodicals, Inc.     

Boosting Activation of Oxygen Molecules on C60 Fullerene by Boron Doping

The activation of oxygen molecules on boron‐doped C₆₀ fullerene (C₅₉B) and the subsequent water formation reaction are systematically investigated by using hybrid density functional calculations. Results indicate that C₅₉B shows a favorable ability to activate oxygen molecules both kinetically and thermodynamically. The oxygen molecule is first adsorbed on the boron atom, which is identified to be the most reactive site in C₅₉B for O₂ adsorption because of its high positive charge and spin density. The adsorption structure C₅₉B?O₂ can further isomerize to form two products with small reaction barriers. Water formation reactions upon these two structures are energetically favorable and suggest a four‐electron mechanism for the oxygen reduction reaction catalyzed by C₅₉B. This work provides a reliable theoretical insight into the catalytic properties of boron‐doped fullerene, which is believed to be helpful to explore fullerene catalysts.     

Quantum chemical study of the autoxidation of ascorbate

Reactions involved in the autoxidation of ascorbate have been investigated with quantum chemical first‐principles and ab initio methods. Reaction energies and Gibbs energies of the reactions were calculated at the density functional theory level applying the gradient‐corrected BP86 and the hybrid B3LYP functionals together with def2‐TZVP basis sets. Results of single‐point CC2, CCSD, and CCSD(T) calculations were used for calibration of the density functional theory data and show excellent agreement with the B3LYP values. Based on the Gibbs energy ascorbic acid AscH₂ is found to be the energetically lowest species in aqueous solution, whereas the monoanion ascorbate AscH is the most abundant one near pH = 7. Asc was found to be the preferred reducing agent for autoxidation and oxidation processes. The results also support a metal‐catalyzed synthesis of the reactive oxygen species H₂O₂ according to a redox cycling mechanism proposed in literature. © 2016 Wiley Periodicals, Inc.     

Effects of zero point vibration on the reaction dynamics of water dimer cations following ionization

Reactions of water dimer cation following ionization have been investigated by means of a direct ab initio molecular dynamics method. In particular, the effects of zero point vibration and zero point energy (ZPE) on the reaction mechanism were considered in this work. Trajectories were run on two electronic potential energy surfaces (PESs) of : ground state (²A″‐like state) and the first excited state (²A′ ‐ like state). All trajectories on the ground‐state PES lead to the proton‐transferred product: H₂O⁺(Wd)‐H₂O(Wa) → OH(Wd)‐H₃O⁺(Wa), where Wd and Wa refer to the proton donor and acceptor water molecules, respectively. Time of proton transfer (PT) varied widely from 15 to 40 fs (average time of PT = 30.9 fs). The trajectories on the excited‐state PES gave two products: an intermediate complex with a face‐to‐face structure (H₂O‐OH₂)⁺ and a PT product. However, the proton was transferred to the opposite direction, and the reverse PT was found on the excited‐state PES: H₂O(Wd)‐H₂O⁺ (Wa) → H₃O⁺(Wd)‐OH(Wa). This difference occurred because the ionizing water molecule in the dimer switched between the ground and excited states. The reaction mechanism of and the effects of ZPE are discussed on the basis of the results. © 2017 Wiley Periodicals, Inc.     

A DFT study on the possibility of using a single Cu atom incorporated nitrogen-doped graphene as a promising and highly active catalyst for oxidation of CO

Using dispersion-corrected density functional theory (DFT) calculations, a single Cu adatom incorporated nitrogen-doped graphene (CuN₃-Gr) is proposed as a new and highly active noble-metal-free catalyst for carbon monoxide (CO) oxidation reaction. According to our results, the Cu adatom can be stably anchored onto the monovavancy site of the nitrogen-doped graphene, and the resulting large diffusion barrier suggests that the metal clustering is avoided in CuN₃-Gr. Three possible reaction mechanisms for CO oxidation (ie, Eley–Rideal, Langmuir–Hinshelwood, and termolecular Eley–Rideal) are systematically studied. It is found that the activation energy for the rate-determining step of the termolecular Eley–Rideal mechanism is only 0.13 eV, which is much smaller than those of others. The results of this study may provide a useful guideline for the design of highly active and promising single-metal catalysts for the CO oxidation reaction based on graphene.     

The solvent effect on two competing reaction mechanisms involving hypervalent iodine reagents (λ3‐iodanes): Facing the limit of the stationary quantum chemical approach

Trifluoromethylation of acetonitrile with 3,3‐dimethyl‐1‐(trifluoromethyl)?1λ³,2‐ benziodoxol is assumed to occur via reductive elimination (RE) of the electrophilic CF₃‐ligand and MeCN bound to the hypervalent iodine. Computations in gas phase showed that the reaction might also occur via an S_N2 mechanism. There is a substantial solvent effect present for both reaction mechanisms, and their energies of activation are very sensitive toward the solvent model used (implicit, microsolvation, and cluster‐continuum). With polarizable continuum model‐based methods, the S_N2 mechanism becomes less favorable. Applying the cluster‐continuum model, using a shell of solvent molecules derived from ab initio molecular dynamics (AIMD) simulations, the gap between the two activation barriers ( ) is lowered to a few kcal mol^?1 and also shows that the activation entropies ( ) and volumes ( ) for the two mechanisms differ substantially. A quantitative assessment of will therefore only be possible using AIMD. A natural bond orbital‐analysis gives further insight into the activation of the CF₃‐reagent by protonation. © 2014 Wiley Periodicals, Inc.     

Low‐energy structures of benzene clusters with a novel accurate potential surface

The benzene‐benzene (Bz‐Bz) interaction is present in several chemical systems and it is known to be crucial in understanding the specificity of important biological phenomena. In this work, we propose a novel Bz‐Bz analytical potential energy surface which is fine‐tuned on accurate ab initio calculations in order to improve its reliability. Once the Bz‐Bz interaction is modeled, an analytical function for the energy of the clusters may be obtained by summing up over all pair potentials. We apply an evolutionary algorithm (EA) to discover the lowest‐energy structures of clusters (for ), and the results are compared with previous global optimization studies where different potential functions were employed. Besides the global minimum, the EA also gives the structures of other low‐lying isomers ranked by the corresponding energy. Additional ab initio calculations are carried out for the low‐lying isomers of and clusters, and the global minimum is confirmed as the most stable structure for both sizes. Finally, a detailed analysis of the low‐energy isomers of the n = 13 and 19 magic‐number clusters is performed. The two lowest‐energy isomers show S₆ and C₃ symmetry, respectively, which is compatible with the experimental results available in the literature. The structures reported here are all non‐symmetric, showing two central Bz molecules surrounded by 12 nearest‐neighbor monomers in the case of the five lowest‐energy structures. © 2015 Wiley Periodicals, Inc.     

Distinguishing and quantifying the torquoselectivity in competitive ring‐opening reactions using the stress tensor and QTAIM

Currently the theories to explain and predict the classification of the electronic reorganization due to the torquoselectivity of a ring‐opening reaction cannot accommodate the directional character of the reaction pathway; the torquoselectivity is a type of stereoselectivity and therefore is dependent on the pathway. Therefore, in this investigation we introduced new measures from quantum theory of atoms in molecules and the stress tensor to clearly distinguish and quantify the transition states of the inward (TSIC) and outward (TSOC) conrotations of competitive ring‐opening reactions of 3‐(trifluoromethyl)cyclobut‐1‐ene and 1‐cyano‐1‐methylcyclobutene. We find the metallicity ξ( r _b) of the ring‐opening bond does not occur exactly at the transition state in agreement with transition state theory. The vector‐based stress tensor response β_σ was used to distinguish the effect of the CN, CH₃, and CF₃ groups on the TSIC and TSOC paths that was consistent with the ellipticity ε, the total local energy density H( r_b ) and the stress tensor stiffness S_σ. We determine the directional properties of the TSIC and TSOC ring‐opening reactions by constructing a stress tensor space with trajectories (s) with length l in real space, longer l correlated with the lowest density functional theory‐evaluated total energy barrier and hence will be more thermodynamically favored. © 2016 Wiley Periodicals, Inc.     

Pt/ZrO2:An Efficient Catalyst for Aerobic Oxidation of Toluene in Aqueous Solution

The heterogeneous oxidation of toluene in aqueous medium has been investigated. Artificially contaminated water with aromatic compound (toluene) was exposed to a simple platinized zirconia (1% Pt/ZrO₂) catalyst in the presence of molecular oxygen. This selective oxidation of toluene to benzyl alcohol, benzaldehyde and benzoic acid provides a step for removing toluene from wastewater or converting it into less harmful substances. Different parameters, e.g. the reaction time, temperature, pressure, the amount of catalyst and agitation, etc influenced the toluene conversion and selectivity. Typical batch reactor kinetic data were obtained and fitted to the classical Langmuir‐Hinshelwood model, Mars‐van Krevelen model as well as to the Eley‐Rideal model of heterogeneously catalyzed reactions. The Eley‐Rideal model was found to give a better fit. 1% Pt/ZrO₂ was observed to be the most active for oxidation of toluene at 333 K in oxygenated atmosphere [p(O₂) ca. 101 kPa] with a nominal stirring speed ≧900 r/min. It was found that catalytic oxidation may be an effective method for the removal of volatile organic compounds from aqueous solutions and comparable to other advanced oxidation processes.     

Structure and electrochemical properties for complexes of nitrocompounds with inorganic ions: A theoretical approach

Reduction and oxidation (redox) reactions are widely used for removal of nitrocompounds from contaminated soil and water. Structures and redox properties for complexes of nitrocompounds, such as 2,4,6‐trinitrotoluene (TNT), 2,4‐dinitrotoluene (DNT), 2,4‐dinitroanisole (DNAN), and 5‐nitro‐2,4‐dihydro‐3H?1,2,4‐triazol‐3‐one (NTO), with common inorganic ions (Na⁺, Cl^?, ) were investigated at the SMD(Pauling)/PCM(Pauling)/MPWB1K/TZVP level of theory. Atoms in molecules (AIM) theory was applied to analyze the topological properties of the bond critical points involved in the interactions between the nitrocompounds and the ions. Topological analyses show that intermolecular interactions of the types O(N)…Na⁺, C‐H…Cl^?( ), and C…Cl^?( ) may be discussed as noncovalent closed‐shell interactions, while N‐H···Cl^?( ) hydrogen bonds are partially covalent in nature. Complexation causes significant decrease of redox activity of the nitrocompounds. Analysis of the reduction potentials of the complexes obtained through application of the Pourbaix diagram of an iron/water system revealed that sodium complexes of NTO might be reduced by metallic iron. © 2016 Wiley Periodicals, Inc.     

Four faces of the interaction between ions and aromatic rings

Non‐covalent interactions between ions and aromatic rings play an important role in the stabilization of macromolecular complexes; of particular interest are peptides and proteins containing aromatic side chains (Phe, Trp, and Tyr) interacting with negatively (Asp and Glu) and positively (Arg and Lys) charged amino acid residues. The structures of the ion–aromatic‐ring complexes are the result of an interaction between the large quadrupole moment of the ring and the charge of the ion. Four attractive interaction types are proposed to be distinguished based on the position of the ion with respect to the plane of the ring: perpendicular cation–π (CP_⊥), co‐planar cation–π (CP_∥), perpendicular anion–π (AP_⊥), and co‐planar anion–π (AP_∥). To understand more than the basic features of these four interaction types, a systematic, high‐level quantum chemical study is performed, using the X^– + C₆H₆, M⁺ + C₆H₆, X^– + C₆F₆, and M⁺ + C₆F₆ model systems with X⁻ = H⁻, F⁻, Cl⁻, HCOO⁻, CH₃COO⁻ and M⁺ = H⁺, Li⁺, Na⁺, , CH₃ , whereby C₆H₆ and C₆F₆ represent an electron‐rich and an electron‐deficient π system, respectively. Benchmark‐quality interaction energies with small uncertainties, obtained via the so‐called focal‐point analysis (FPA) technique, are reported for the four interaction types. The computations reveal that the interactions lead to significant stabilization, and that the interaction energy order, given in kcal mol⁻¹ in parentheses, is CP_⊥ (23–37) > AP_⊥ (14–21) > CP_∥ (9–22) > AP_∥ (6–16). A natural bond orbital analysis performed leads to a deeper qualitative understanding of the four interaction types. To facilitate the future quantum chemical characterization of ion–aromatic‐ring interactions in large biomolecules, the performance of three density functional theory methods, B3LYP, BHandHLYP, and M06‐2X, is tested against the FPA benchmarks, with the result that the M06‐2X functional performs best. © 2017 Wiley Periodicals, Inc.     

Theoretical study on monometallic cyanide cluster fullerenes YCN@C72

The geometries, stabilities, and electronic properties of new endohedral fullerene YCN@C₇₂ have been investigated by the B3LYP and PBE1PBE density functional (DFT) methods. The C_2v(11188)‐C₇₂ cage, which violates the isolated pentagon rule (IPR) with a pair of fused pentagons, is predicted to be the lowest energy isomer for both empty and YCN@C₇₂. The relatively large HOMO‐LUMO gap (B3LYP: 1.48 eV, PBE1PBE: 1.68 eV) for YCN@C_2v(11188)‐C₇₂ reveals this structure kinetic stability. Significantly, the encased YCN cluster adopts a triangular structure inside the C_2v(11188)‐C₇₂ cage, similar to the results reported on YCN@C_s(6)‐C₈₂ and TbCN@C₂(5)‐C₈₂. Furthermore, the vertical ionization potential and electron affinity, UV‐vis‐NIR and IR spectra of YCN@C_2v(11188)‐C₇₂ have been predicted to facilitate future experimental characterization. © 2015 Wiley Periodicals, Inc.     

Quantum Monte Carlo with very large multideterminant wavefunctions

An algorithm to compute efficiently the first two derivatives of (very) large multideterminant wavefunctions for quantum Monte Carlo calculations is presented. The calculation of determinants and their derivatives is performed using the Sherman–Morrison formula for updating the inverse Slater matrix. An improved implementation based on the reduction of the number of column substitutions and on a very efficient implementation of the calculation of the scalar products involved is presented. It is emphasized that multideterminant expansions contain in general a large number of identical spin‐specific determinants: for typical configuration interaction‐type wavefunctions the number of unique spin‐specific determinants ( ) with a non‐negligible weight in the expansion is of order . We show that a careful implementation of the calculation of the N_det ‐dependent contributions can make this step negligible enough so that in practice the algorithm scales as the total number of unique spin‐specific determinants, , over a wide range of total number of determinants (here, N_det up to about one million), thus greatly reducing the total computational cost. Finally, a new truncation scheme for the multideterminant expansion is proposed so that larger expansions can be considered without increasing the computational time. The algorithm is illustrated with all‐electron fixed‐node diffusion Monte Carlo calculations of the total energy of the chlorine atom. Calculations using a trial wavefunction including about 750,000 determinants with a computational increase of ～400 compared to a single‐determinant calculation are shown to be feasible. © 2016 Wiley Periodicals, Inc.     

Development of a new parameter optimization scheme for a reactive force field based on a machine learning approach

Reactive molecular dynamics (MD) simulation is performed using a reactive force field (ReaxFF). To this end, we developed a new method to optimize the ReaxFF parameters based on a machine learning approach. This approach combines the k-nearest neighbor and random forest regressor algorithm to efficiently locate several possible ReaxFF parameter sets. As a pilot test of the developed approach, the optimized ReaxFF parameter set was applied to perform chemical vapor deposition (CVD) of an α-Al₂O₃ crystal. The crystal structure of α-Al₂O₃ was reasonably reproduced even at a relatively high temperature (2000 K). The reactive MD simulation suggests that the (110) surface grows faster than the (0001) surface, indicating that the developed parameter optimization technique could be used for understanding the chemical reaction in the CVD process. © 2019 Wiley Periodicals, Inc.     

Extension of accompanying coordinate expansion and recurrence relation method for general‐contraction basis sets

An algorithm of the accompanying coordinate expansion and recurrence relation (ACE‐RR), which is used for the rapid evaluation of the electron repulsion integral (ERI), has been extended to the general‐contraction (GC) scheme. The present algorithm, denoted by GC‐ACE‐RR, is designed for molecular calculations including heavy elements, whose orbitals consist of many primitive functions with and without higher angular momentum such as d‐ and f‐orbitals. The performance of GC‐ACE‐RR was assessed for ‐, ‐, ‐, and ‐type ERIs in terms of contraction length and the number of GC orbitals. The present algorithm was found to reduce the central processing unit time compared with the ACE‐RR algorithm, especially for higher angular momentum and highly contracted orbitals. Compared with HONDOPLUS and GAMESS program packages, GC‐ACE‐RR computations for ERIs of three‐dimensional gold clusters Au_n (n = 1, 2, …, 10, 15, 20, and 25) are more than 10 times faster. © 2014 Wiley Periodicals, Inc.