Potential Energy Calculations Research Articles

Mechanistic Insights into the Palladium-Catalyzed Perfluoroalkylative Carbonylation of Unactivated Alkenes to β-Perfluoroalkyl Esters: A DFT Study.

Transition metal-catalyzed multicomponent carbonylation is an efficient synthetic strategy to access multifunctional esters in high yields with broad functional group tolerance and good chemoselectivity. Considering the development of highly efficient synthetic methods for esters, it remains significant to grasp the mechanism of constructing multifunctional esters. Herein, density functional theoretical calculations were carried out to acquire mechanistic insight into the synthesis of β-perfluoroalkyl esters from a specific palladium-catalyzed perfluoroalkylative carbonylation of unactivated alkenes using carbon monoxide. A detailed mechanistic understanding of this reaction route includes (1) multistep radical reaction process, (2) C-C coupling and CO insertion, (3) ligand exchange, and (4) Pd-based intermediate oxidation and reductive elimination. The multistep radical process was fundamentally rationalized, including Rf· formation and radicals A and E from unactivated alkene and CO oxidation, respectively. The potential energy calculation indicated that the CO insertion into the perfluorinated alkyl radicals preceded Pd-catalyzed oxidation in the competitively multistep free radical reaction process. In addition, the I-/PhO- exchange step was predicted to be spontaneous to products. The IGMH analysis further attested to the reductive elimination process involved in the rate-determining step. Thus, a simple and valid density functional theory (DFT) approach was developed to reveal the multistep radical mechanism for the Pd-catalyzed perfluoroalkylative carbonylation of unactivated alkenes to access functional β-perfluoroalkyl esters.

Systematic study of two proton radioactivity within the effective liquid drop model

In this study, we investigated two-proton radioactivity using the effective liquid drop model with varying mass asymmetry shapes and effective inertia coefficients (VMAS-EFF). Gaudin’s expression term for Coulomb potential energy is replaced in the current study’s calculation of potential energy. The VMAS-EFF combination predicts the half-life with the lowest standard deviation ( σ =1.03) compared to other models and previous constant mass asymmetry with Werner-inertial Wheeler’s coefficient combinations. The lowest standard deviation value indicates that the VMAS-EFF combination is suitable for reproducing the experimental data. We extended the half-life predictions to another 54 nuclei and compared them with six theoretical model predictions and two empirical formula predictions. The present work also investigated the decay possibilities using quantum tunnelling by computing the driving potential (V-Q) for various states of angular momentum l = 0, 2, 3, and 4. Found that 6Be, 6B, 8C, 12O,15,16Ne, 19Mg, 22Si, 26S, 30Ar 38,39Ti, 40V, 42Cr, 45Fe, 48,49Ni, 54Zn, 58,59,60Ge and 64Se nuclei have a high chance of emission for two protons, while 7B, 10N, 14F, 17Na, 24P, 28Cl,32K, 34Ca, 36,37Sc, 44Mn, 47Co, 52Cu, 56,57,58Ga, 61,62As nuclei have a lower chance for two proton than one proton decay. The computation of separation energy findings agree well with the driving potential findings.

A case study of an extreme flooding episode in Charikar, Eastern Afghanistan

Abstract This work investigates the meteorological mechanisms forming a classical frontal system on 26 August 2020 in the northeast and eastern parts of Afghanistan. The weather system caused heavy rainfall and led to severe flash floods. Flooding, affected by torrential rain showers, struck mostly the city of Charikar in Parvan province early in the morning day, while most people were asleep. This caused 150 deaths, and nearly 500 houses were destroyed. This research explores atmospheric processes by examining the National Centers for Environmental Prediction dataset and MERRA Model database. The calculation of the convective available potential energy (CAPE) and Showalter index extracted from the Skew-T log-pressure diagram shows a high value of the CAPE at around 2,632 J/kg and −6.6 for the Showalter index, respectively. This presents a very extreme instability in the study area during the time of the flood. The study reveals that the triggering of this system was mostly by thermodynamical aspects, low-level deep convergence, and local topographical aspects rather than the PV streamer. However, the anomaly climate analysis for different atmospheric elements with a comparison of the climate normal values shows the importance of climate change in the weather system into a stronger frontal activity associated with stronger baroclinicity over the study area.

Understanding the Multifaceted Mechanism of Compound I Formation in Unspecific Peroxygenases through Multiscale Simulations.

Unspecific peroxygenases (UPOs) can selectively oxyfunctionalize unactivated hydrocarbons by using peroxides under mild conditions. They circumvent the oxygen dilemma faced by cytochrome P450s and exhibit greater stability than the latter. As such, they hold great potential for industrial applications. A thorough understanding of their catalysis is needed to improve their catalytic performance. However, it remains elusive how UPOs effectively convert peroxide to Compound I (CpdI), the principal oxidizing intermediate in the catalytic cycle. Previous computational studies of this process primarily focused on heme peroxidases and P450s, which have significant differences in the active site from UPOs. Additionally, the roles of peroxide unbinding in the kinetics of CpdI formation, which is essential for interpreting existing experiments, have been understudied. Moreover, there has been a lack of free energy characterizations with explicit sampling of protein and hydration dynamics, which is critical for understanding the thermodynamics of the proton transport (PT) events involved in CpdI formation. To bridge these gaps, we employed multiscale simulations to comprehensively characterize the CpdI formation in wild-type UPO from Agrocybe aegerita (AaeUPO). Extensive free energy and potential energy calculations were performed in a quantum mechanics/molecular mechanics setting. Our results indicate that substrate-binding dehydrates the active site, impeding the PT from H2O2 to a nearby catalytic base (Glu196). Furthermore, the PT is coupled with considerable hydrogen bond network rearrangements near the active site, facilitating subsequent O-O bond cleavage. Finally, large unbinding free energy barriers kinetically stabilize H2O2 at the active site. These findings reveal a delicate balance among PT, hydration dynamics, hydrogen bond rearrangement, and cosubstrate unbinding, which collectively enable efficient CpdI formation. Our simulation results are consistent with kinetic measurements and offer new insights into the CpdI formation mechanism at atomic-level details, which can potentially aid the design of next-generation biocatalysts for sustainable chemical transformations of feedstocks.

Prion-like Aggregation of the Heptapeptide GNNQQNY into Amyloid Nanofiber Is Governed by Configuration Entropy.

A major cause of prion infectivity is the early formation of small, fibril-like aggregates consisting of the heptapeptide GNNQQNY. The prion aggregates exhibit a unique stacking mode in which the hydrophobic tyrosine (Y) is exposed outward, forming a bilayer β-sheet-stacking zipper structure. This stacking mode of the prion peptides, termed "Y-outward" structure for convenience, goes against the common understanding that, for other amyloid-forming peptides, the hydrophobic residues should be hidden within the peptide fibril, referred to as "Y-inward" structure. To explore the extraordinary stacking behaviors of the prion GNNQQNY peptides, two fibril models are constructed in a fashion of "Y-outward" and "Y-inward" stackings and then studied in silico to examine their thermodynamic stabilities and disaggregation pathways. The "Y-inward" structure indeed exhibits stronger thermodynamic stability than the "Y-outward" structure, according to potential energy and stacking energy calculations. To show how the peptide fibrils dissociate, we illustrated two disaggregation pathways. A dihedral-based free energy landscape was then calculated to examine the conformational degrees of freedom of the GNNQQNY chains in the "Y-outward" and "Y-inward" structures. Peptide chains lose more configurational entropy in the "Y-inward" structure than in the "Y-outward" structure, indicating that the prion peptides are prone to aggregate in a fashion of "Y-outward" stacking pattern due to its low conformational constraints. The prion-like aggregation of the GNNQQNY peptides into amyloid fibrils is primarily governed by the configuration entropy.

Neural network learned Pauli potential for the advancement of orbital-free density functional theory.

The Pauli kinetic energy functional and its functional derivative, termed Pauli potential, play a crucial role in the successful implementation of orbital-free density functional theory for electronic structure calculations. However, the exact forms of these two quantities are not known. Therefore, perforce, one employs the approximate forms for the Pauli functional or Pauli potential for performing orbital-free density functional calculations. In the present study, we developed a feed-forward neural network-based representation for the Pauli potential using a 1-dimensional (1-D) model system. We expanded density in terms of basis functions, and the coefficients of the expansion were used as input to a feed-forward neural network. Using the neural network-based representation of the Pauli potential, we calculated the ground-state densities of the 1-D model system by solving the Euler equation. We calculated the Pauli kinetic energy using the neural network-based Pauli potential employing the exact relation between the Pauli kinetic energy functional and the potential. The sum of the neural network-based Pauli kinetic energy and the von Weizsäcker kinetic energy resulted in an accurate estimation of the total kinetic energy. The approach presented in this paper can be employed for the calculation of Pauli potential and Pauli kinetic energy, obviating the need for a functional derivative. The present study is an important step in the advancement of application of machine learning-based techniques toward the orbital-free density functional theory-based methods.

Effect of resolution enhancement using metal ion assisted strategy based on electrospray ionization-ion mobility spectrometry: A case study of carbendazim and thiabendazole in fruits

A method for the rapid and simultaneous determination of carbendazim and thiabendazole residues by electrospray ionization-ion mobility spectrometry (ESI-IMS) combined with a metal ion-assisted technique was developed and validated in different fruit matrices. The metal ion assisted strategy was performed instead of tedious pre-separation procedures to overcome the limitation of low resolution of IMS. Four transition metal cations, Co(II), Ni(II), Cu(II), and Zn(II), were screened and their interactions with carbendazim and thiabendazole were investigated. The injection flow rate and metal ion concentration were optimized. The Cu(II) assisted approach helped to achieve well-separated peaks with a peak-to-peak resolution of 3.61. This method was then applied to detect carbendazim and thiabendazole simultaneously in apples, pears, bananas, and mangoes. The limit of detection (LOD) were 0.03 mg kg−1 and 0.13 mg kg−1 for carbendazim and thiabendazole, respectively, while spiked recoveries were 61.5–122.0% and 83.5–119.8%, respectively, with RSDs less than 13.9%. These satisfactory evaluation parameters indicated that the approach was capable of performing quantitative analysis of multi-pesticide residues. In addition, the feasibility of using metal ion assisted-ESI-IMS for the simultaneous detection also was theoretically demonstrated through molecular electrostatic potential analysis and binding energy calculation based on density functional theory (DFT). Both experimental and theoretical results revealed the effectiveness of the metal ion assisted strategy in improving the resolution of ESI-IMS.

Density functional study of atomic arrangements in CrMnFeCoNi high-entropy alloy and their impact on vacancy formation energy and segregation

Using the density functional theory-coupled Monte Carlo approach, we explored the chemical short-range order (SRO) and element segregation in equimolar CrMnFeCoNi alloy. We found that state-of-the-art approximation of random element distribution is only applicable at > 1100 K close to the melting temperature, while the Cr-Cr repulsion driving the system stabilization and accompanying the formation of cubic Cr sublattice, and mild Ni-Ni attraction are the most prominent pair interactions at lower temperatures. Chemical potential and vacancy formation energy calculations indicate that Cr is most sensitive to the local chemical environment, making Cr atoms most stabilized when the preferred SRO is introduced. While the vacancy formation is predicted equally probable among five constituting elements in the random solid solution, Cr and Ni atoms show the lowest vacancy formation energies in the structure with SRO. Furthermore, distinct element segregation was predicted in the vicinity of planar defects, including symmetric tilt grain boundary and stacking fault, which we correlated to the site- and chemistry-dependent atomic volume and bond lengths. It suggests that the local mechanical strain and bond energy induce the SRO development and element segregation: Namely, the system takes advantage of segregation of Ni atoms having large atomic volume or Cr-Cr pairs having elongated bond lengths to fill in the excess volume at defects that relaxes the mechanical strain field and optimizes bond energy distribution. The correlation between the SRO and properties of CrMnFeCoNi alloy needs further investigations, which is expected to greatly help understand and control the properties of high-entropy alloys.

A 2D pillared-layer Co-based MOF as a “two-in-one” chemosensor for S2- with meticulous chemodosimetric screening of HSO4- in absolute aqueous medium and photo-induced thiol-ene for CO2 conversion

Herein, we have designed a new Co(II)-based MOF, {[Co(1,4-NDC)(4,4′-BPY)(H2O)2].H2O}∞ (Co-NDC-BPY) by using mixed ligands 1,4-napthalenedicarboxylic acid (1,4-NDC) and 4,4′-bipyridine (4,4′-BPY). Interestingly, the MOF can selectively and discriminatively detect S2- and HSO4- from purely aqueous medium via mutually independent mechanism with prompt response (∼6 s) at very low detection thresholds of 29.9 μM and 9.4 μM for S2- and HSO4-, respectively. In the presence of S2-, “turn-off” fluorescence response is perceived via static quenching due to facilitation of photoinduced electron transfer (PET) process via ground state complexation. On the other hand, protic anion, HSO4- systematically enhanced the fluorescence at 435 nm via releasing the co-ligand. Moreover, detection from several field-water samples with good recovery, demonstrates the real-world applicability of this Co-NDC-BPY MOF. To the best of our knowledge, this is the first MOF based chemosensor, which could discriminatively detect HSO4- and S2- from fully aqueous solutions. Additionally, this MOF exhibits excellent catalytic activity in the CO2 fixation on epoxides. The potential energy calculation suggests the possible mechanistic pathway for this cycloaddition reaction. As it possesses a moderately low band gap with n-type conductivity, this Co-NDC-BPY MOF is also explored as photocatalyst in thiol-ene chemistry for the synthesis of thiol-ether bridged bis-carbonate from allyl-glycidyl carbonate monomer, which is a platform chemical for the synthesis of valuable polymers.

Dissociation of edge and screw pyramidal I and II dislocations in magnesium

Pyramidal dislocations in magnesium (Mg) and other hexagonal close-packed metals play an important role in accommodating plastic strains along the c-axis. Bulk single crystal Mg only presents very limited plasticity in c-axis compression, and this behavior was attributed to out-of-plane dissociation of pyramidal dislocations onto the basal plane and resulted in an immobile dislocation configuration. In contrast, other simulations and experiments reported in-plane dissociation of pyramidal dislocations on their slip planes. Thus, the core structure and mode of dissociation of pyramidal dislocations are still not well understood. To better understand the dissociation behavior of pyramidal dislocations in Mg at room temperature, in this work, atomistic simulations were conducted to investigate four types of pyramidal dislocations at 300 K: edge and screw Py-I on {101¯1}, edge and screw Py-II on {112¯2} by using a modified embedded atom method (MEAM) potential for Mg and anisotropic elasticity dislocation model. The results show that when energy minimization was performed before relaxation, in-plane dissociation of edge dislocations on respective pyramidal plane could be obtained at room temperature for all four types of dislocation. Without energy minimization, the edge dislocations dissociated out-of-plane onto the basal plane. Calculations of potential energy and hydrostatic stress of individual atoms at the edge dislocation core show that the extraordinarily high energy and atomic stresses in the as-constructed dislocation structures caused the out-of-plane dissociation onto the basal plane. The core structures of all four types of pyramidal dislocation after in-plane dissociation were analyzed by computing the distribution of the Burgers vector.

Probing the water mediated proton transfer in histidine tautomerization

Histidine tautomerism plays a key role in the aggregation of amyloid peptides, which is important for understanding the origin of Alzheimer’s disease as well as its diagnosis and treatment. Herein, density functional theory calculations were performed using explicit water molecules and joint implicit/explicit water cluster models to explore the catalytic mechanism and the key role of water assistance effect in the histidine tautomerization reaction. To clarify the proton transfer mechanism involved in histidine tautomerization, three to five water molecules were used to catalyze the proton transfer process governing the transition between the histidine tautomers. Potential energy calculations showed that hiε·(H2O)n tautomerism proceeds via a single proton transfer pathway. Systematic analyses of the hydrogen bonds and charge distribution of the key components indicated that tautomerism can be promoted by reducing the number of assistant water molecules or involving the joint implicit/explicit water solvent effect. This study provides theoretical insights into the mechanism of water-assisted histidine isomerization as it relates to the Aβ aggregation hypothesis of Alzheimer’s disease.

Metal Ion-induced Gelation of High-concentration Graphite-like Crystalline Nanosheet Aqueous Suspensions.

The stability and transformation of nanomaterial aqueous suspensions are essential for their applications. Preparation of high-concentration carbon nanomaterials suspensions remains challenging due to their nonpolar nature. Herein, 200mgmL-1 carbon nanomaterial aqueous suspensions are achieved by using graphite-like crystalline nanosheets (GCNs) with high hydrophilicity. Furthermore, these high-concentration GCN aqueous suspensions spontaneously transform into gels when induced by mono-, di-, and trivalent metal salt electrolytes at room temperature. Theoretical calculation of potential energy by DLVO theory reveals that the gelatinized GCNs is a new and metastable state between two usual forms of solution and coagulation. It is shown that the gelation of GCNs is due to the preferential orientation of nanosheets in an edge-edge arrangement, which differs from the case of solution and coagulation. High-temperature treatment of GCN gels produces metal/carbon materials with pore structures. This work provides a promising opportunity to create various metal/carbon functional materials.

Spectroscopic Properties of the Alkali-Krypton Diatomic M-Kr (M = Rb, Cs, and Fr) van der Waals Systems Including the Spin-Orbit Coupling.

Using an ab initio approach based on pseudopotential technique, pair potential approach, core polarization potentials, and large Gaussian basis sets, we investigate interaction of heavy alkali-krypton diatomic M-Kr (M = Rb, Cs, and Fr) van der Waals dimers. In this context, the core-core interactions for M+-Kr (M = Rb, Cs, and Fr) are calculated at coupled-cluster single and double excitation (CCSD) level and included in the total potential energy. Therefore, the potential energy curves are performed for 14 electronic states: eight of 2Σ+ symmetry, four of 2Π symmetry, and two of 2Δ symmetry. Furthermore, for each M-Kr dimer, the spin-orbit coupling has been considered for the B2Σ+, A2Π, 32Σ+, 22Π, 52Σ+, 32Π, and 12Δ states. In addition, the transition dipole moment has been determined, including the spin-orbit effect using the rotational matrix issued from the spin-orbit potential energy calculations.

Study on the initial pyrolysis kinetics of strained polycyclic hydrocarbons

Strained polycyclic hydrocarbons are one of the most important classes of high-energy density fuels. In this work, the thermodynamics and initial pyrolysis kinetics of five strained polycyclic hydrocarbons, which are isomers of JP-10 and are linearly aggregates of two cyclopropyl rings and one cyclobutyl ring, were investigated using quantum chemical computations. The initial pyrolysis reactions include ring bond breaking and bridge bond breaking. The ring bond breaking reactions include a diradical pathway which is the direct C-C bond breaking to produce a diradical and an isomerization pathway involving concert bond breaking and H-atom transfer, and the bridge bond breaking reactions lead to two radicals. Our potential energy calculation shows that the ring bond breaking reactions are much more energetically favorable than the bridge bond breaking reactions, which can be neglected in the initial pyrolysis process of strained polycyclic hydrocarbons. The rate constants of the ring bond breaking reactions were computed using variational transition state theory (VTST) or transition state theory (TST). Our calculated results demonstrated that ring bond breaking reactions of the three-membered ring are competitive with that of the four-membered ring. The studied reactions are divided into classes depending on the size of the rings (three- or four-membered ring) and the types of the carbon atoms of the breaking C-C bond (Cs-Cs, Cs-Ct, Ct-Ct and Cq-Cs). Reaction rate rules are established for each class, which are useful for the mechanism generation for analogous strained polycyclic hydrocarbons. Thermodynamic properties including net calorific values per mole, gravimetric net heat of combustion and impulse time of our studied strained polycyclic hydrocarbons are higher than those of JP-10. A comparison of the initial pyrolysis kinetics of our studied strained polycyclic hydrocarbons with the isomer JP-10 indicates that these compounds may be easier to pyrolyze.

Enhancing Hit Discovery in Virtual Screening through Absolute Protein-Ligand Binding Free-Energy Calculations.

In the hit identification stage of drug discovery, a diverse chemical space needs to be explored to identify initial hits. Contrary to empirical scoring functions, absolute protein-ligand binding free-energy perturbation (ABFEP) provides a theoretically more rigorous and accurate description of protein-ligand binding thermodynamics and could, in principle, greatly improve the hit rates in virtual screening. In this work, we describe an implementation of an accurate and reliable ABFEP method in FEP+. We validated the ABFEP method on eight congeneric compound series binding to eight protein receptors including both neutral and charged ligands. For ligands with net charges, the alchemical ion approach is adopted to avoid artifacts in electrostatic potential energy calculations. The calculated binding free energies correlate with experimental results with a weighted average of R2 = 0.55 for the entire dataset. We also observe an overall root-mean-square error (RMSE) of 1.1 kcal/mol after shifting the zero-point of the simulation data to match the average experimental values. Through ABFEP calculations using apo versus holo protein structures, we demonstrated that the protein conformational and protonation state changes between the apo and holo proteins are the main physical factors contributing to the protein reorganization free energy manifested by the overestimation of raw ABFEP calculated binding free energies using the holo structures of the proteins. Furthermore, we performed ABFEP calculations in three virtual screening applications for hit enrichment. ABFEP greatly improves the hit rates as compared to docking scores or other methods like metadynamics. The good performance of ABFEP in rank ordering compounds demonstrated in this work confirms it as a useful tool to improve the hit rates in virtual screening, thus facilitating hit discovery.

Crystal morphology prediction of CL-20 and 1,4-DNI co-crystal at different temperatures.

The morphologies of hexanitrohexaazaisowurtzitane (CL-20) and 1,4-dinitroimidazole (1,4-DNI) co-crystal under vacuum or solvent at different temperatures were predicted. The CL-20/1,4-DNI co-crystal has six important growth crystal planes: (002), (011), (101), (11‒1), (110), (111). The areas of (002), (101), and (011) planes account for a relatively large proportion, which are important crystal planes that affect the crystal morphology. The crystal habits at different temperatures were simulated. The simulation results showed that the crystal plane attachment energy of CL-20 and 1,4-DNI co-crystal increases with the increase of temperature, indicating that the increase of temperature is conducive to the growth of crystal planes. The aspect ratio decreases with the increase of temperature and the morphology of co-crystal becomes more spherical at a higher temperature. The theoretical predictions are in good agreement with the experiment. The simulation results can provide guidance for the crystallization of CL-20/1,4-DNI to obtain a nearly spherical crystal morphology. The CL-20/1,4-DNI unit cell structure was geometrically optimized by the COMPASS force field. The AE model was used to predict the morphology of CL-20/1,4-DNI under vacuum, resulting in the most morphologically important growth planes. Ethyl acetate was selected as the solvent. The interaction energy between the solvent and the crystal plane, and the attachment energies in solvent at 298 K, 320 K, 340 K, 360 K, and 380 K were predicted. The NVT ensemble is used in the molecular dynamics calculation process. The simulation step is 1 fs and the total simulation time is 500 ps. The Andersen thermostat is selected as the temperature control method. In the potential energy calculation, the atom-based and Ewald methods were selected to calculate the van der Waals force and the electrostatic interaction force, respectively.

A rod- and tessellation-based comparative analysis of polymorphic and structurally-invariant molecular crystals: application to sulfathiazole and 2-benzyl-5-benzylidenecyclopentanones.

A rationalization of the alternative crystal structures adopted by a given molecular compound or by a set of substitutionally related molecular compounds is provided by reference to the five known polymorphs of sulfathiazole and 16 substituted 2-benzyl-5-benzylidene cyclopentanones (BBCPs), respectively. Two-dimensional (2D) packing fractions (ϕ2D) take space-group symmetry into account, with a clear demarcation of closed-packed zones (CPZ) and molecular junction zones (JZ) in all Z' = 1 structures. Representation of the molecules as two linked rods allows a concise treatment of conformation and rapid visualization of crystal packing. Combined with calculations of intermolecular potential energies, the rod method provides insight into the stabilization mechanisms of alternative polymorphs. In sulfathiazole, the primary factor is to obtain satisfactory hydrogen bonding, with close packing a secondary consideration. In BBCP derivatives, by comparison, close packing is the primary mechanism of stabilization. Whereas the 2D structures arising in CPZ can be analysed as tessellations of molecular-based cells, a method based on 2D Dirichlet cells is required for the JZ. These are calculated from the centroids of the molecular envelopes in high-symmetry planes. It is shown that these centroid coordinates, when combined with space-group symmetry and unit cell coordinates, provide a concise parameterization of all structures containing JZ. It is anticipated that this parameterization may be exploited to predict such crystal structures from powder diffraction data.

Radiationless deactivation pathways versus H-atom elimination from the N-H bond photodissociation in PhNH2-(Py)n (n = 1,2) complexes.

Minimum energy structures of the ground and lowest excited states of aniline (PhNH2) solvated by pyridine (Py) show that the clusters formed are stabilized by hydrogen bonds in which only one or both hydrogen atoms of the NH2 group take part. Two different N-H bonds photodissociation in PhNH2-(Py)n (n = 1,2) complexes, free and hydrogen bonded have been studied by analyzing excited state potential energy surfaces. In the first one, only N-H bonds engaged in hydrogen bonding in these complexes are considered. RICC2 calculations of potential energy (PE) profiles indicate that all photochemical reaction paths along N-H stretching occur mainly via the proton-coupled electron transfer (PCET) mechanism. The repulsive charge transfer 1ππ*(CT) state dominates the PE profiles, leading to low-lying 1ππ*(CT)/S0 conical intersections and thus provide channels for ultrafast radiationless deactivation of the electronic excitation or stabilization to biradical complexes. The second photoreaction consists of a direct dissociation along the free N-H bond of the NH2 group. It has been shown that this process is played by excited singlet states of 1πσ* character having repulsive potential energy profiles with respect to the stretching of N-H bond, which dissociates over an exit barrier about 0.5eV giving rise to the formation of a 1πσ*/S0 conical intersection. This may cause an internal conversion to the ground state or may lead to H-atom elimination. This photophysical process is the same in both planar and T-shaped conformers of the PhNH2-Py monomer complex. Our findings reveal that there is no single dominating path in the photodissociation of N-H bonds in PhNH2-(Py)n complexes, but rather a variety of paths involving H-atom elimination and several quenching mechanisms.

Clustering and Microscopically Separated States Formation in Fission Potential Energy Calculations

Clustering and Microscopically Separated States Formation in Fission Potential Energy Calculations

Efficient electrocatalytic reduction of NO to ammonia on BC3 nanosheets

Searching for an economical and highly efficient electrocatalytic reduction catalyst for ammonia synthesis under controllable conditions is a very attractive and challenging subject in chemistry. In this study, we systematically studied the electrocatalytic performance of BC3 nanosheets as potential NO reduction reaction (NORR) electrocatalysts using density functional theory (DFT) calculations. It was found that BC3 two-dimensional (2D) materials exhibit excellent catalytic activity with a very low limiting potential of −0.29/-0.11 V along three reaction paths. The total reaction is NO (g)+5H++5e−→NH3(g)+ H2O. The density of states of adsorbed NO, NH3, and the corresponding crystal orbital hamiltonian population (COHP) analysis revealed the mechanism of NO being activated and the reasons for NH3 adsorption/desorption on the surface of BC3. The reaction path, limiting potential, and Gibbs free energy calculations of BC3 catalyzed NO to ammonia synthesis revealed that for path 1, the potential-determining step is *NO+H++e−→*NOH, and for path 2/3 the potential-determining step is *NO+(H++e−)→*HNO. Calculation of the thermodynamic energy barriers for NO dissociation at the BC3 surface and NO hydrogenation reveals that NO is more likely to be hydrogenated rather than dissociated. The influences of the proton-electron hydrogenation site on the process of ammonia synthesis in the key reduction step were analyzed by Bader charge analysis and charge density, it is pointed out that the electronic structure and affects the reaction process can be controlled by hydrogenation at different sites of intermediates. These results pave the way for using nitrogen oxides not just nitrogen as raw materials for ammonia synthesis with 2D materials.