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Understanding how water ligands regulate the conformational changes and functionality of the oxygen-evolving complex (OEC) in photosystem II (PSII) throughout the catalytic cycle of oxygen evolution remains a highly intriguing and unresolved challenge. In this study, we investigate the effect of water insertion (WI) on the redox state of the OEC by using the molecular dynamics (MD) and quantum mechanics/molecular mechanics (QM/MM) hybrid methods. We find that water binding significantly reduces the free energy change for proton-coupled electron transfer (PCET) from Mn to YZ•, underscoring the important regulatory role of water binding, which is essential for enabling the OEC redox-leveling mechanism along the catalytic cycle. We propose a water binding mechanism in which WI is thermodynamically favored by the closed-cubane form of the OEC, with water delivery mediated by Ca2+ligand exchange. Isomerization from the closed- to open-cubane conformation at three post-WI states highlights the importance of the location of the MnIIIcenter in the OEC and the orientation of its Jahn–Teller axis to conformational changes of the OEC, which might be critical for the formation of the O–O bond. These findings reveal a complex interplay between conformational changes in the OEC and the ligand environment during the activation of the OEC by YZ•. Analogous regulatory effects due to water ligand binding are expected to be important for a wide range of catalysts activated by redox state transitions in aqueous environments.

A well-known catalyst, fac-Re(4,4′-R2-bpy)(CO)3Cl (bpy = bipyridine; R = COOH) (ReC0A), has been widely studied for CO2reduction; however, its photocatalytic performance is limited due to its narrow absorption range. Quantum dots (QDs) are efficient light harvesters that offer several advantages, including size tunability and broad absorption in the solar spectrum. Therefore, photoinduced CO2reduction over a broad range of the solar spectrum could be enabled by ReC0A catalysts heterogenized on QDs. Here, we investigate interfacial electron transfer from Cd3P2QDs to ReC0A complexes covalently bound on the QD surface, induced by photoexcitation of the QD. We explore the effect of triethylamine, a sacrificial hole scavenger incorporated to replenish the QD with electrons. Through combined transient absorption spectroscopic and computational studies, we demonstrate that electron transfer from Cd3P2to ReC0A can be enhanced by a factor of ∼4 upon addition of triethylamine. We hypothesize that the rate enhancement is a result of triethylamine possibly altering the energetics of the Cd3P2–ReC0A system by interacting with the quantum dot surface, deprotonation of the quantum dot, and preferential solvation, resulting in a shift of the conduction band edge to more negative potentials. We also observe the rate enhancement in other QD–electron acceptor systems. Our findings provide mechanistic insights into hole scavenger–quantum dot interactions and how they may influence photoinduced interfacial electron transfer processes.

We detail the development of the first enantioselective synthetic route to euonyminol (1), the most heavily oxidized member of the dihydro-β-agarofuran sesquiterpenes and the nucleus of the macrocyclic alkaloids known as the cathedulins. Key steps in the synthetic sequence include a novel, formal oxyalkylation reaction of an allylic alcohol by [3 + 2] cycloaddition; a tandem lactonization–epoxide opening reaction to form the trans-C2–C3 vicinal diol residue; and a late-stage diastereoselective trimethylaluminum-mediated α-ketol rearrangement. We report an improved synthesis of the advanced unsaturated ketone intermediate 64by means of a 6-endo-dig radical cyclization of the enyne 42. This strategy nearly doubled the yield through the intermediate steps in the synthesis and avoided a problematic inversion of stereochemistry required in the first-generation approach. Computational studies suggest that the mechanism of this transformation proceeds via a direct 6-endo-trig cyclization, although a competing 5-exo-trig cyclization, followed by a rearrangement, is also energetically viable. We also detail the challenges associated with manipulating the oxidation state of late-stage intermediates, which may inform efforts to access other derivatives such as 9-epi-euonyminol or 8-epi-euonyminol. Our successful synthetic strategy provides a foundation to synthesize the more complex cathedulins.

We address the protonation state of the water-derived ligands in the oxygen-evolving complex (OEC) of photosystem II (PSII), prepared in the S2state of the Kok cycle. We perform quantum mechanics/molecular mechanics calculations of isotropic proton hyperfine coupling constants, with direct comparisons to experimental data from two-dimensional hyperfine sublevel correlation (HYSCORE) spectroscopy and extended X-ray absorption fine structure (EXAFS). We find a low-barrier hydrogen bond with significant delocalization of the proton shared by the water-derived ligand, W1, and the aspartic acid residue D1–D61 of the D1 polypeptide. The lowering of the zero-point energy of a shared proton due to quantum delocalization precludes its release to the lumen during the S1→ S2transition. Retention of the proton facilitates the shuttling of a proton during the isomerization of the tetranuclear manganese–calcium–oxo (Mn4Ca–oxo) cluster, from the “open” to “closed” conformation, a step suggested to be necessary for oxygen evolution from previous studies. Our findings suggest that quantum-delocalized protons, stabilized by low-barrier hydrogen bonds in model catalytic systems, can facilitate the accumulation of multiple oxidizing equivalents at low overpotentials.

Effective methane utilization for either clean power generation or value-added chemical production has been a subject of growing attention worldwide for decades, yet challenges persist mostly in relation to methane activation under mild conditions. Here, we report hematite, an earth-abundant material, to be highly effective and thermally stable to catalyze methane combustion at low temperatures (<500 °C) with a low light-off temperature of 230 °C and 100% selectivity to CO2. The reported performance is impressive and comparable to those of precious-metal-based catalysts, with a low apparent activation energy of 17.60 kcal·mol–1. Our theoretical analysis shows that the excellent performance stems from a tetra-iron center with an antiferromagnetically coupled iron dimer on the hematite (110) surface, analogous to that of the methanotroph enzyme methane monooxygenase that activates methane at ambient conditions in nature. Isotopic oxygen tracer experiments support a Mars van Krevelen redox mechanism where CH4is activated by reaction with a hematite surface oxygen first, followed by a catalytic cycle through a molecular-dioxygen-assisted pathway. Surface studies with in situdiffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and density functional theory (DFT) calculations reveal the evolution of reaction intermediates from a methoxy CH3–O–Fe, to a bridging bidentate formate b-HCOO–Fe, to a monodentate formate m-HCOO–Fe, before CO2is eventually formed via a combination of thermal hydrogen-atom transfer (HAT) and proton-coupled electron transfer (PCET) processes. The elucidation of the reaction mechanism and the intermediate evolutionary profile may allow future development of catalytic syntheses of oxygenated products from CH4in gas-phase heterogeneous catalysis.

The selective adsorption of light alkane over alkene on ZIF-7 provides a new insight for the separation of small-sized molecules with similar physical properties. To gain a comprehensive understanding of the separation selectivity of alkane over alkene on ZIF-7, we systematically investigated the adsorption and diffusion processes of C2H6and C2H4on ZIF-7 by periodic density functional theory calculations with a standard generalized gradient approximation functional [Perdew−Burke−Ernzerhof (PBE)], PBE with Grimme’s D2 and D3 corrections for dispersion, and four van der Waals density functionals (vdW-DFs). We found that because of a stronger dispersion interaction and more number of C–H···π/N/H bonds of C2H6in the ZIF-7 framework compared to that of C2H4, C2H6has always obviously more favorable adsorption energy than C2H4at potential adsorption sites and needs to conquer a lower free energy barrier than C2H4during the transport in ZIF-7. The stronger dispersion interaction between C2H6and ZIF-7 could be ascribed to the larger molecular surface of C2H6and the fitness of its molecular shape to the cavity structure of ZIF-7. These findings indicate that the preferential adsorption and quicker diffusion of C2H6on ZIF-7 determine that ZIF-7 with structural flexibility can be utilized for the separation of C2H6/C2H4mixture. Our calculations highlight the principle of structural matching for the preferential adsorption: the threefold symmetry of C2H6fits favorably with the symmetry of the local structure of the adsorption site to form a more stable complex, which is mainly bound through dispersion force. It may provide useful guidance for the rational design of porous materials for the separation of small guest molecules.

Water oxidation is the key kinetic bottleneck of photoelectrochemical devices for fuel synthesis. Despite advances in the identification of intermediates, elucidating the catalytic mechanism of this multi-redox reaction on metal–oxide photoanodes remains a significant experimental and theoretical challenge. Here, we report an experimental analysis of water oxidation kinetics on four widely studied metal oxides, focusing particularly on haematite. We observe that haematite is able to access a reaction mechanism that is third order in surface-hole density, which is assigned to equilibration between three surface holes and M(OH)–O–M(OH) sites. This reaction exhibits low activation energy (Ea≈ 60 meV). Density functional theory is used to determine the energetics of charge accumulation and O–O bond formation on a model haematite (110) surface. The proposed mechanism shows parallels with the function of the oxygen evolving complex of photosystem II, and provides new insights into the mechanism of heterogeneous water oxidation on a metal oxide surface.

The performance of a photoelectrochemical (PEC) system is highly dependent on the charge separation, transport and transfer characteristics at the photoelectrode|electrolyte interface. Of the factors that influence the charge behaviors, the crystalline facets of the semiconductor in contact with the electrolyte play an important role but has been poorly studied previously. Here, we present a study aimed at understanding how the different facets of hematite affect the charge separation and transfer behaviors in a solar water oxidation reaction. Specifically, hematite crystallites with predominantly {012} and {001} facets exposed were synthesized. Density functional theory (DFT) calculations revealed that hematite {012} surfaces feature higher OH coverage, which was confirmed by X-ray photoelectron spectroscopy (XPS). These surface OH groups act as active sites to mediate water oxidation reactions, which plays a positive role for the PEC system. These surface OH groups also facilitate charge recombination, which compromises the charge separation capabilities of hematite. Indeed, intensity modulated photocurrent spectroscopy (IMPS) confirmed that hematite {012} surfaces exhibit higher rate constants for both charge transfer and recombination. Open circuit potential (OCP) measurements revealed that the hematite {012} surface exhibits a greater degree of Fermi level pinning effect. Our results shed light on how different surface crystal structures may change surface kinetics and energetics. The information is expected to contribute to efforts on optimizing PEC performance for practical solar fuel synthesis.

Heterogeneous catalysts with atomically defined active centers hold great promise for high-performance applications. Among them, catalysts featuring active moieties with more than one metal atom are important for chemical reactions that require synergistic effects but are rarer than single atom catalysts (SACs). The difficulty in synthesizing such catalysts has been a key challenge. Recent progress in preparing dinuclear heterogeneous catalysts (DHCs) from homogeneous molecular precursors has provided an effective route to address this challenge. Nevertheless, only side-on bound DHCs, where both metal atoms are affixed to the supporting substrate, have been reported. The competing end-on binding mode, where only one metal atom is attached to the substrate and the other metal atom is dangling, has been missing. Here, we report the first observation that end-on binding is indeed possible for Ir DHCs supported on WO3. Unambiguous evidence supporting the binding mode was obtained by in situdiffuse reflectance infrared Fourier transform spectroscopy and high-angle annular dark-field scanning transmission electron microscopy. Density functional theory calculations provide additional support for the binding mode, as well as insights into how end-on bound DHCs may be beneficial for solar water oxidation reactions. The results have important implications for future studies of highly effective heterogeneous catalysts for complex chemical reactions.

Copper oxides have been of considerable interest as electrocatalysts for CO2reduction (CO2R) in aqueous electrolytes. However, their role as an active catalyst in reducing the required overpotential and improving the selectivity of reaction compared with that of polycrystalline copper remains controversial. Here, we introduce the use of selected-ion flow tube mass spectrometry, in concert with chronopotentiometry, in situ Raman spectroscopy, and computational modeling, to investigate CO2R on Cu2O nanoneedles, Cu2O nanocrystals, and Cu2O nanoparticles. We show experimentally that the selective formation of gaseous C2products (i.e., ethylene) in CO2R is preceded by the reduction of the copper oxide (Cu2OR) surface to metallic copper. On the basis of density functional theory modeling, CO2R products are not formed as long as Cu2O is present at the surface because Cu2OR is kinetically and energetically more favorable than CO2R.

The design and development of materials for electrochemical energy storage and conversion devices requires fundamental understanding of chemical interactions at electrode/electrolyte interfaces. For Li–S batteries that hold the promise for outperforming the current generation of Li ion batteries, the interactions of lithium polysulfide (LPS) intermediates with the electrode surface strongly influence the efficiency and cycle life of the sulfur cathode. While metal oxides have been demonstrated to be useful in trapping LPS, the actual binding modes of LPS on 3d transition metal oxides and their dependence on the metal element identity across the periodic table remain poorly understood. Here, we investigate the chemical interactions between LPS and oxides of Mn, Fe, Co, and Cu by combining X-ray photoelectron spectroscopy and density functional theory calculations. We find that Li–O interactions dominate LPS binding to the oxides (Mn3O4, Fe2O3, and Co3O4), with increasing strength from Mn to Fe to Co. For Co3O4, LPS binding also involves metal–sulfur interactions. We also find that the metal oxides exhibit different binding preferences for different LPS, with Co3O4binding shorter-chain LPS more strongly than Mn3O4. In contrast to the other oxides, CuO undergoes intense reduction and dissolution reactions upon interaction with LPS. The reported findings are thus particularly relevant to the design of LPS/oxide interfaces for high-performance Li–S batteries.

Conventional time-dependent density functional theory (TDDFT) is based on a closed-shell Kohn–Sham (KS) singlet ground state with the adiabatic approximation, using either linear response (KS-LR) or the Tamm–Dancoff approximation (KS-TDA); these methods can only directly predict singly excited states. This deficiency can be overcome by using a triplet state as the reference in the KS-TDA approximation and “exciting” the singlet by a spin flip (SF) from the triplet; this is the method suggested by Krylov and co-workers, and we abbreviate this procedure as SF-KS-TDA. SF-KS-TDA can be applied either with the original collinear kernel of Krylov and co-workers or with a noncollinear kernel, as suggested by Wang and Ziegler. The SF-KS-TDA method does bring some new practical difficulties into play, but it can at least formally model doubly excited states and states with double-excitation character, so it might be more useful than conventional TDDFT (both KS-LR and KS-TDA) for photochemistry if these additional difficulties can be surmounted and if it is accurate with existing approximate exchange–correlation functionals. In the present work, we carried out calculations specifically designed to understand better the accuracy and limitations of the conventional TDDFT and SF-KS-TDA methods; we did this by studying closed-shell atoms and closed-shell monatomic cations because they provide a simple but challenging testing ground for what we might expect in studying the photochemistry of molecules with closed-shell ground states. To test their accuracy, we applied conventional KS-LR and KS-TDA and 18 versions of SF-KS-TDA (nine collinear and nine noncollinear) to the same set of vertical excitation energies (including both Rydberg and valence excitations) of Be, B+, Ne, Na+, Mg, and Al+. We did this for 10 exchange–correlation functionals of various types, both local and nonlocal. We found that the GVWN5 and M06 functionals with nonlocal kernels in spin-flip calculations can both have accuracy competitive to CASPT2 calculations. When the results were averaged over all 36 test energy differences, seven (GVWN5, M06, B3PW91, LRC-ωPBE, LRC-ωPBEh, PBE, and M06-2X) of the 10 studied density functionals had smaller mean unsigned errors for noncollinear calculations than the mean unsigned error of the best functional (M06-2X) for either conventional KS-TDA or KS-LR.

We present a new method for fitting potential energy surfaces in molecular-mechanics-like internal coordinates based on data from electronic structure calculations. The method should be applicable to chemical reactions involving either bond dissociation or isomerization and is illustrated here for bond dissociation, in particular the breaking of an O–H bond in methanol and the breaking of an N–H bond in dimethylamine. As compared to previously available systematic methods for fitting global potential energy surfaces, it extends the maximum size of the system than can be treated by at least an order of magnitude.

The 3d-series transition metals (also called the fourth-period transition metals), Sc to Zn, are very important in industry and biology, but they provide unique challenges to computing the electronic structure of their compounds. In order to successfully describe the compounds by theory, one must be able to describe their components, in particular the constituent atoms and cations. In order to understand the ingredients required for successful computations with density functional theory, it is useful to examine the performance of various exchange–correlation functionals; we do this here for 4sN3dN′transition-metal atoms and their cations. We analyze the results using three ways to compute the energy of the open-shell states: the direct variational method, the weighted-averaged broken symmetry (WABS) method, and a new broken-symmetry method called the reinterpreted broken symmetry (RBS) method. We find the RBS method to be comparable in accuracy with the WABS method. By examining the overall accuracy in treating 18 multiplicity-changing excitations and 10 ionization potentials with the RBS method, 10 functionals are found to have a mean-unsigned error of <5 kcal/mol, with ωB97X-D topping the list. For local density functionals, which are more practical for extended systems, the M06-L functional is the most accurate. And by combining the results with our previous studies of p-block and 4d-series elements as well as databases for alkyl bond dissociation, main-group atomization energies, and π–π noncovalent interactions, we find five functionals, namely, PW6B95, MPW1B95, M08-SO, SOGGA11-X, and MPWB1K, to be highly recommended. We also studied the performance of PW86 and C09 exchange functionals, which have drawn wide interest in recent studies due to their claimed ability to reproduce Hartree–Fock exchange at long distance. By combining them with four correlation functionals, we find the performance of the resulting functionals disappointing both for 3d transition-metal chemistry and in broader tests, and thus we do not recommend PW86 and C09 as components of generalized gradient approximations for general application.

Complete-active-space self-consistent-field (CASSCF) calculations provide useful reference wave functions for configuration interaction or perturbation theory calculations of excited-state potential energy surfaces including dynamical electron correlation. However, the canonical molecular orbitals (MOs) of CASSCF calculations usually have mixed character in regions of strong interaction of two or more electronic states; therefore, they are unsuitable for diabatization using the configurational uniformity approach. Here, CASSCF diabatic MOs for phenol have been obtained by the 4-fold way, and comparison to the CASSCF canonical MOs shows that they are much smoother. Using these smooth CASSCF diabatic MOs, we performed direct diabatization calculations for the three low-lying states (1ππ, 1ππ*, and 1πσ*) and their diabatic (scalar) couplings at the dynamically correlated multiconfiguration quasidegenerate perturbation theory (MC-QDPT) level. We present calculations along the O–H stretching and C–C–O–H torsion coordinates for the nonadiabatic photodissociation of phenol to the phenoxyl radical and hydrogen atom. The seams of 1ππ*/1πσ* and 1ππ/1πσ* diabatic crossings are plotted as functions of these coordinates. We also present diabatization calculations for displacements along the out-of-plane ring distortion modes 16a and 16b of the phenyl group. The dominant coupling modes of the two conical intersections (1ππ*/1πσ* and 1ππ/1πσ*) are discussed. The present diabatization method is confirmed to be valid even for significantly distorted ring structures by diabatization calculations along a reaction path connecting the planar equilibrium geometry of phenol to its strongly distorted prefulvenic form. The present work provides insight into the mode specificity of phenol photodissociation and shows that diabatization at the MC-QDPT level employing CASSCF diabatic MOs can be a good starting point for multidimensional dynamics calculations of photochemical reactions.

We examine the accuracy of single-reference and multireference correlated wave function methods for predicting accurate energies and potential energy curves of biradicals. The biradicals considered are intermediate species along the bond dissociation coordinates for breaking the F–F bond in F2, the O–O bond in H2O2, and the C–C bond in CH3CH3. We apply a host of single-reference and multireference approximations in a consistent way to the same cases to provide a better assessment of their relative accuracies than was previously possible. The most accurate method studied is coupled cluster theory with all connected excitations through quadruples, CCSDTQ. Without explicit quadruple excitations, the most accurate potential energy curves are obtained by the single-reference RCCSDt method, followed, in order of decreasing accuracy, by UCCSDT, RCCSDT, UCCSDt, seven multireference methods, including perturbation theory, configuration interaction, and coupled-cluster methods (with MRCI+Q being the best and Mk-MR-CCSD the least accurate), four CCSD(T) methods, and then CCSD.

The emission spectrum of the 0–0 band of theC2Σ+–X2Π transition for12CH and13CH isotopic molecules have been obtained using a Geissler tube. The spectra have been photographed under high resolution and calibrated against Th standard lines. The reduction of the spectra for the individual bands has been performed via a nonlinear least-squares fit with the effective Hamiltonian of Brown. New values of the molecular constants for upper state have been determined. The 0–0 band of theC2Σ+–X2Π system in the13CH radical has been obtained and analyzed for the first time.

The use of surgical techniques is described for the management of dysfunctional uterine bleeding by endometrial ablation as alternatives to hysterectomy. Current approaches include the neodymium yttrium aluminium garnet (Nd:YAG) laser and resection by electrosurgery using a ball-end electrode. Of 484 patients treated since 1985, 361 (74%) became amenorrhoeic with only occasional spotting 68 (14%) reported satisfactory results with 55 (12%) reporting an unsatisfactory outcome.

In the emission spectrum of the nitric oxide molecule 13 bands of the γ system (A²Σ⁺–X²Π) were recorded and analyzed. The following bands of this system comprising over 3950 lines were photographed under high resolution by using conventional spectroscopy and Th standard lines: 0–0 through 0–6 and 1–4, 1–5, 2–0, 2–6, 2–7, and 3–4. The analysis of the individual bands and the merged analysis of the entire band system made it possible to unify, extend, and improve the information about the γ system and the energy structure of its participating statesA²Σ⁺andX²Π. RKR turning points of theAandXstates and Franck–Condon factors andrcentroids for theA–Xsystem were also determined using the precise molecular parameters obtained in the present work.

It is demonstrated that the energy loss features within the XPS spectra, which have generally been regarded as a nuisance, can be used to obtain useful secondary information.

A high resolution scanning Auger electron microscope with an X‐ray analysis system is used to study the surface chemistry of inclusion groups in stainless steel 316 relative to the bulk composition.

Competing Interests: The authors declare that there are no conflicts of interest.