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Kanemaru, Kodai; Watanabe, Yoshihiro; Yoshida, Norio; Nakano, Haruyuki
doi: 10.1002/jcc.27009pmid: 36190170
A combined method of the Dirac–Hartree–Fock (DHF) method and the reference interaction‐site model (RISM) theory is reported; this is the initial implementation of the coupling of the four‐component relativistic electronic structure theory and an integral equation theory of molecular liquids. In the method, the DHF and RISM equations are solved self‐consistently, and therefore the electronic structure of the solute, including relativistic effects, and the solvation structure are determined simultaneously. The formulation is constructed based on the variational principle with respect to the Helmholtz energy, and analytic free energy gradients are also derived using the variational property. The method is applied to the iodine ion (I−), methyl iodide (CH3I), and hydrogen chalcogenide (H2X, where X = O–Po) in aqueous solutions, and the electronic structures of the solutes, as well as the solvation free energies and their component analysis, solvent distributions, and solute–solvent interactions, are discussed.
Dong, Shizhi; Li, Yanshuai; Hu, Hongyu; Li, Ruichuan; Yan, Bing; Zhang, Xing; Wang, Zeliang; Zhang, Jinyu; Guo, Lin
doi: 10.1002/jcc.27010pmid: 36169382
The hydrogen evolution effect of ZrS2 carrier loaded with transition metal single‐atom (SA) was explored by first‐principles method. ZrS2 was constructed with transition metal single‐atom and dual‐atom. The structure–activity relationship of supported single‐atom catalysts was described by electronic properties and hydrogen evolution kinetics. The results show that the ZrS2 carrier‐loaded atomic‐level catalysts are more likely to occur in acidic environments, where the Mo SA load has a higher hydrogen precipitation capacity than the Pt SA. In the case of dual‐atom adsorption, most of the hydrogen reduction processes are higher than that of single atom loading, which indicates that the outer orbital hybridization is more likely to lead to the interfacial charge recombination of the catalyst. Thereinto, Ni/Pt @ZrS2 has the lowest Gibbs free energy (0.08 eV), and the synergistic effect of transition metals induces the deviation of the center of the d‐band from the Fermi level and improves the dissociation ability of H ions. The design provides a new catalytic model for the HER and provides some ideas for understanding the two‐site catalysis.
Ramos‐Sánchez, Pablo; Harvey, Jeremy N.; Gámez, José A.
doi: 10.1002/jcc.27011pmid: 36239971
Algorithms that automatically explore the chemical space have been limited to chemical systems with a low number of atoms due to expensive involved quantum calculations and the large amount of possible reaction pathways. The method described here presents a novel solution to the problem of chemical exploration by generating reaction networks with heuristics based on chemical theory. First, a second version of the reaction network is determined through molecular graph transformations acting upon functional groups of the reacting. Only transformations that break two chemical bonds and form two new ones are considered, leading to a significant performance enhancement compared to previously presented algorithm. Second, energy barriers for this reaction network are estimated through quantum chemical calculations by a growing string method, which can also identify non‐octet species missed during the previous step and further define the reaction network. The proposed algorithm has been successfully applied to five different chemical reactions, in all cases identifying the most important reaction pathways.
Gorantla, Sai Manoj N. V. T.; Karnamkkott, Harsha S.; Arumugam, Selvakumar; Mondal, Sangita; Mondal, Kartik Chandra
doi: 10.1002/jcc.27012pmid: 36169176
The factors/structural features which are responsible for the binding, activation and reduction of N2 to NH3 by FeMoco of nitrogenase have not been completely understood well. Several relevant model complexes by Holland et al. and Peters et al. have been synthesized, characterized and studied by theoretical calculations. For a matter of fact, those complexes are much different than real active N2‐binding Fe‐sites of FeMoco, which possesses a central C(4‐) ion having an eight valence electrons as an μ6‐bridge. Here, a series of [(S3C(0))Fe(II/I/0)‐N2]n‐ complexes in different charged/spin states containing a coordinated σ‐ and π‐donor C(0)‐atom which possesses eight outer shell electrons [carbone, (Ph3P)2C(0); Ph3P→C(0)←PPh3] and three S‐donor sites (i.e. ‐S‐Ar), have been studied by DFT, QTAIM, and EDA‐NOCV calculations. The effect of the weak field ligand on Fe‐centres and the subsequent N2‐binding has been studied by EDA‐NOCV analysis. The role of the oxidation state of Fe and N2‐binding in different charged and spin states of the complex have been investigated by EDA‐NOCV analyses. The intrinsic interaction energies of the Fe−N2 bond are in the range from −42/−35 to −67 kcal/mol in their corresponding ground states. The S3C(0) donor set is argued here to be closer to the actual coordination environment of one of the six Fe‐centres of nitrogenase. In comparison, the captivating model complexes reported by Holland et al. and Peter et al. possess a stronger π‐acceptor C‐ring (S2Cring donor, π‐C donor) and stronger donor set like CP3 (σ‐C donor) ligands, respectively.
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