Reaction energetics on long‐range corrected density functional theory: Diels–Alder reactions

The possibility of quantitative reaction analysis on the orbital energies of long‐range corrected density functional theory (LC‐DFT) is presented. First, we calculated the Diels–Alder reaction enthalpies that have been poorly given by conventional functionals including B3LYP functional. As a result, it is found that the long‐range correction drastically improves the reaction enthalpies. The barrier height energies were also computed for these reactions. Consequently, we found that dispersion correlation correction is also crucial to give accurate barrier height energies. It is, therefore, concluded that both long‐range exchange interactions and dispersion correlations are essentially required in conventional functionals to investigate Diels–Alder reactions quantitatively. After confirming that LC‐DFT accurately reproduces the orbital energies of the reactant and product molecules of the Diels–Alder reactions, the global hardness responses, the halves of highest occupied molecular orbital (HOMO)‐lowest unoccupied molecular orbital (LUMO) energy gaps, along the intrinsic reaction coordinates of two Diels–Alder reactions were computed. We noticed that LC‐DFT results satisfy the maximum hardness rule for overall reaction paths while conventional functionals violate this rule on the reaction pathways. Furthermore, our results also show that the HOMO‐LUMO gap variations are close to the reaction enthalpies for these Diels–Alder reactions. Based on these results, we foresee quantitative reaction analysis on the orbital energies. © 2012 Wiley Periodicals, Inc.     

Luminescence quenching by reversible ionization or exciplex formation/dissociation

The kinetics of fluorescence quenching by both charge transfer and exciplex formation is investigated, with an emphasis on the reversibility and nonstationarity of the reactions. The Weller elementary kinetic scheme of bimolecular geminate ionization and the Markovian rate theory are shown to lead to identical results, provided the rates of the forward and backward reactions account for the numerous recontacts during the reaction encounter. For excitation quenching by the reversible exciplex formation, the Stern-Volmer constant is specified in the framework of the integral encounter theory. The bulk recombination affecting the Stern-Volmer quenching constant makes it different for pulse excited and stationary luminescence. The theory approves that the free energy gap laws for ionization and exciplex formation are different and only the latter fits properly the available data (for lumiflavin quenching by aliphatic amines and aromatic donors) in the endergonic region.     

Visible‐Light‐Induced Organic Photochemical Reactions through Energy‐Transfer Pathways

Visible‐light photocatalysis is a rapidly developing and powerful strategy to initiate organic transformations, as it closely adheres to the tenants of green and sustainable chemistry. Generally, most visible‐light‐induced photochemical reactions occur through single‐electron transfer (SET) pathways. Recently, visible‐light‐induced energy‐transfer (EnT) reactions have received considerable attentions from the synthetic community as this strategy provides a distinct reaction pathway, and remarkable achievements have been made in this field. In this Review, we highlight the most recent advances in visible‐light‐induced EnT reactions.     

Energy gap law of electron transfer in nonpolar solvents

We investigate the energy gap law of electron transfer in nonpolar solvents for charge separation and charge recombination reactions. In polar solvents, the reaction coordinate is given in terms of the electrostatic potentials from solvent permanent dipoles at solutes. In nonpolar solvents, the energy fluctuation due to solvent polarization is absent, but the energy of the ion pair state changes significantly with the distance between the ions as a result of the unscreened strong Coulomb potential. The electron transfer occurs when the final state energy coincides with the initial state energy. For charge separation reactions, the initial state is a neutral pair state, and its energy changes little with the distance between the reactants, whereas the final state is an ion pair state and its energy changes significantly with the mutual distance; for charge recombination reactions, vice versa. We show that the energy gap law of electron-transfer rates in nonpolar solvents significantly depends on the type of electron transfer.     

Reactive orbital energy theory serving a theoretical foundation for the electronic theory of organic chemistry

It is established that the reactive orbital energy theory (ROET) theoretically reproduces the rule-based electronic theory diagrams of organic chemistry by a comparative study on the charge transfer natures of typical organic carbon–carbon and carbon–heteroatom bond formation reactions: aldol, Mannich, α-aminooxylation, and isogyric reactions. The ROET, which is an expansion of the reaction electronic theories (e.g., the frontier orbital theory) in terms of orbital energies, elucidates the reactive orbitals driving reactions and the charge transferability indices of the reactions. Performing the ROET analyses of these reactions shows that the charge transfer directions given in the rule-based diagrams of the electronic theory are reproduced even for the functional groups of charge transfer destinations in all but only two processes for 38 reaction processes. The ROET analyses also make clear the detailed orbital-based pictures of these bond formation reactions: that is, the use of the out-of-plane antibonding π orbitals in acidic conditions (enol-mode) and in-plane antibonding π orbitals in basic conditions (enolate-mode), which explain the experimentally assumed mechanisms such as the π-bond formations in acidic conditions and σ-bond formations at α-carbons in basic conditions. Furthermore, the ROET analyses explicate that the methyl group initially accepts electrons and then donates them to the bond formations in the target reactions. It is, consequently, suggested that the ROET serves a theoretical foundation for the electronic theory of organic chemistry.     

A DFT study of Diels-Alder reactions of o-quinone methides and various substituted ethenes: selectivity and reaction mechanism

The Diels-Alder (DA) reactions of various substituted ethenes (methyl vinyl ether (MVE), styrene, and methyl vinyl ketone (MVK)) with o-quinone methides (o-QM) are studied by means of density functional theory (DFT) at the B3LYP/6-31G(d,p) level. On the basis of analysis for frontier molecular orbital and comparison of the activation energies for different reaction pathways, the ortho attack modes present transition structures more stable than the meta ones. The reactivity, ortho selectivity, and asynchronicity are enhanced with the increase of the electron-releasing character of the substitute on ethene fragment. The discussions for the charge distribution and charge transfer on different transition states indicate that there are different molecular mechanisms for the different substituted ethenes. The calculations show that the effect of solvent decreases the activation energy and increases the asynchronicity. The results also indicate that the hydrogen-bond formation between chloroform and the carbonyl oxygen of the o-QM lowers the activation energies and increases the asynchronicity.     

An automated method for graph-based chemical space exploration and transition state finding

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.     

Theoretical study of CH…O hydrogen bond in proton transfer reaction of glycine

Density functional theory (DFT) calculations are used to study the strength of the CH…O H‐bond in the proton transfer reaction of glycine. Comparison has been made between four proton transfer reactions (ZW1, ZW2, ZW3, SCRFZW) in glycine. The structural parameters of the zwitterionic, transition, and neutral states of glycine are strongly perturbed when the proton transfer takes place. It has been found that the interaction of water molecule at the side chain of glycine is high in the transition state, whereas it is low in the zwitterionic and neutral states. This strongest multiple hydrogen bond interaction in the transition state reduces the barrier for the proton transfer reaction. The natural bond orbital analysis have also been carried out for the ZW2 reaction path, it has been concluded that the amount of charge transfer between the neighboring atoms will decide the strength of H‐bond. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Synthesis of Alternating Donor–Acceptor Ladder‐Type Molecules and Investigation of Their Multiple Charge‐Transfer Pathways

We describe the synthesis as well as the optical and charge‐transport properties of a series of donor–acceptor (D‐A) ladder‐type heteroacenes. These molecules are stable, soluble, and contain up to 24 fused rings. Structural analyses indicated that the backbones of S 10r and Se 10r are bent in single crystals. The three 10‐ring heteroacenes were functionalized with thiol anchoring groups and used for single‐molecular conductance measurements. The highest conductance was observed for molecular wires containing a benzoselenadiazole (BSD) moiety, which exhibits the narrowest band gap. Multiple charge‐transport pathways were observed in molecular wires containing either benzothiadiazole (BTD) or BSD. The conductance is a complex function of both energy gap and orbital alignment.     

Proton‐Coupled Electron Transfer Reactions Catalysed by 3 d Metal Complexes

Proton‐coupled electron transfer (PCET) reactions are essential for a wide range of natural energy‐conversion reactions and recently, the impact of PCET pathways has been exploited in artificial systems, too. The Minireview highlights PCET reactions catalysed by first‐row transition‐metal complexes, with a focus on the water oxidation, the oxygen reduction, the hydrogen evolution, and the CO₂ reduction reaction. Special attention will be paid to systems in which the impact of such pathways is deduced by comparison to systems with “electron‐only”‐transfer pathways.     

电化学析氢反应诱导的电荷传递SERS效应(英文)

应用高灵敏度的共焦显微拉曼技术 ,分别研究了水体系和不同pH值的硫脲体系中电化学反应与表面增强拉曼散射 (SERS)效应之间的关系 .研究结果表明 ,在电化学析氢反应电位区 ,电荷转移增强机制起主要作用 ,使表面物种的拉曼强度显著地增强 .     

Aligning Electronic and Protonic Energy Levels of Proton‐Coupled Electron Transfer in Water Oxidation on Aqueous TiO2

The high overpotential in water oxidation on anodes is a limiting factor for the large‐scale application of photoelectrochemical cells. To overcome this limitation, it is essential to understand the four proton‐coupled electron transfer (PCET) steps in the reaction mechanism and their implications to the overpotential. Herein, a simple scheme to compute the energies of the PCET steps in water oxidation on the aqueous TiO₂ surface using a hybrid density functional is described. An energy level diagram for fully decoupled electron‐ and proton‐transfer reactions in which both electronic and protonic levels are placed on the same potential scale is also described. The level diagram helps to visualize the electronic and protonic components of the overpotential, and points out what are needed to improve. For TiO₂, it is found that its catalytic activity is due to aligning the protonic energy levels in the PCET steps, while improving the activity requires also aligning the electronic levels.     

FMO‐MD Simulations on the Hydration of Formaldehyde in Water Solution with Constraint Dynamics

Full‐quantum mechanical fragment molecular orbital‐based molecular dynamics (FMO‐MD) simulations were applied to the hydration reaction of formaldehyde in water solution under neutral conditions. Two mechanisms, a concerted and a stepwise one, were considered with respect to the nucleophilic addition and the proton transfer. Preliminary molecular orbital calculations by means of polarized continuum model reaction field predicted that the hydration prefers a concerted mechanism. Because the calculated activation barriers were too high for free FMO‐MD simulations to give reactive trajectories spontaneously, a More O’Ferrall–Jencks‐type diagram was constructed from the statistical analysis of the FMO‐MD simulations with constraint dynamics. The diagram showed that the hydration proceeds through a zwitterionic‐like (ZW‐like) structure. The free energy changes along the reaction coordinate calculated by means of the blue moon ensemble for the hydration and the amination of formaldehyde indicated that the hydration proceeds through a concerted process through the ZW‐like structure, whereas the amination goes through a stepwise mechanism with a ZW intermediate. In inspection of the FMO‐MD trajectories, water‐mediated cyclic proton transfers were observed in both reactions on the way from the ZW‐like structure to the product. These proton transfers also have an asynchronous character, in which deprotonation from the nucleophilic oxygen atom (or nitrogen atom for amination) precedes the protonation of the carbonyl oxygen atom. The results showed the strong advantage of the FMO‐MD simulations to obtain detailed information at a molecular level for solution reactions.     

Source of Cooperativity in Halogen‐Bonded Haloamine Tetramers

Inspired by the isostructural motif in α‐bromoacetophenone oxime crystals, we investigated halogen–halogen bonding in haloamine quartets. Our Kohn–Sham molecular orbital and energy decomposition analysis reveal a synergy that can be traced to a charge‐transfer interaction in the halogen‐bonded tetramers. The halogen lone‐pair orbital on one monomer donates electrons into the unoccupied σ*_N?X orbital on the perpendicular N?X bond of the neighboring monomer. This interaction has local σ symmetry. Interestingly, we discovered a second, somewhat weaker donor–acceptor interaction of local π symmetry, which partially counteracts the aforementioned regular σ‐symmetric halogen‐bonding orbital interaction. The halogen–halogen interaction in haloamines is the first known example of a halogen bond in which back donation takes place. We also find that this cooperativity in halogen bonds results from the reduction of the donor–acceptor orbital‐energy gap that occurs every time a monomer is added to the aggregate.     

Computational investigation of TiSin (n=2-15) clusters by the density-functional theory

The geometries, stabilities, and electronic properties of TiSin (n=2-15) clusters with different spin configurations have been systematically investigated by using density-functional theory approach at B3LYP/LanL2DZ level. According to the optimum TiSin clusters, the equilibrium site of Ti atom gradually moves from convex to surface, and to a concave site as the number of Si atom increases from 2 to 15. When n=12, the Ti atom in TiSi12 completely falls into the center of the Si outer frame, forming metal-encapsulated Si cages, which can be explained by using 16-electron rule. On the basis of the optimized geometries, various energetic properties are calculated for the most stable isomers of TiSin clusters, including the average binding energy, the highest occupied molecular orbital and lowest unoccupied molecular orbital (HOMO-LUMO) gap, fragmentation energy, and the second-order difference of energy. It is found that at size n=6,8,12 the clusters are more stable than neighboring ones. According to the Mulliken charge population analysis, charges always transfer from Si atoms to Ti atom. Furthermore, the HOMO-LUMO gaps of the most stable TiSin clusters are usually smaller than those of Sin clusters.     

Intramolecular Charge Transfer of Carotene‐porphyrin‐fullerene Triad: Sequential or Superexchange Cechanism

As an excellent artificial photosynthetic reaction center, the carotene (C)‐porphyrin (P)‐fullerene (F) triad was extensively investigated experimentally. To reveal the mechanism of the intramolecular charge transfer (ICT) on the mimic of photosynthetic solar energy conversion (such as singlet energy transfer between pigments, and photoinduced electron transfer from excited singlet states to give long‐lived charge‐separated states), the ICT mechanisms of C‐P‐F triad on the exciton were theoretically studied with quantum chemical methods as well as the 2D and 3D real space analysis approaches. The results of quantum chemical methods reveal that the excited states are the ICT states, since the densities of HOMO are localized in the carotene or porphyrin unit, and the densities of LUMO are localized in the fullerene unit. Furthermore, the excited states should be the intramolecular superexchange charge transfer (ISCT) states for the orbital transition from the HOMO whose densities are localized in the carotene to the LUMO whose densities are localized in the fullerene unit. The 3D charge difference densities can clearly show that some excited states are ISCT excited states, since the electron and hole are resident in the fullerene and carotene units, respectively. From the results of the electron‐hole coherence of the 2D transition density matrix, not only 3D results are supported, but also the delocalization size on the exciton can be observed. These phenomena were further interpreted with non‐linear optical effect. The large changes of the linear and non‐linear polarizabilities on the exciton result in the charge separate states, and if their changes are large enough, the ICT mechanism can become the ISCT on the exciton.     

Bis(aminoaryl) Carbon‐Bridged Oligo(phenylenevinylene)s Expand the Limits of Electronic Couplings

Carbon‐bridged bis(aminoaryl) oligo(para ‐phenylenevinylene)s have been prepared and their optical, electrochemical, and structural properties analyzed. Their radical cations are class III and class II mixed‐valence systems, depending on the molecular size, and they show electronic couplings which are among the largest for the self‐exchange reaction of purely organic molecules. In their dication states, the antiferromagnetic coupling is progressively tuned with size from quinoidal closed‐shell to open‐shell biradicals. The data prove that the electronic coupling in the radical cations and the singlet–triplet gap in the dications show similar small attenuation factors, thus allowing charge/spin transfer over rather large distances.     

Binding at molecule/gold transport interfaces. V. Comparison of different metals and molecular bridges

The geometric and electronic structural properties of symmetric and asymmetric metal cluster-molecule-cluster' complexes have been explored. The metals include Au, Ag, Pd, and Al, and both benzenedithiol and the three isometric forms of dicyanobenzene are included as bridging molecules. Calculated properties such as cluster-molecule interface geometry, electronic state, degree of metal --> molecule charge transfer, metal-molecule mixing in the highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) energy region, the HOMO-LUMO gap, cluster --> cluster' charge transfer as a function of external field strength and direction, and the form of the potential profile across such complexes have been examined. Attempts are made to correlate charge transport with the characteristics of the cluster-complex systems. Indications of rectification in complexes that are asymmetric in the molecule, clusters, and molecule-cluster interfaces are discussed. The results obtained here are only suggestive because of the limitations of the cluster-complex model as it relates to charge transport.     

Different catalysis role of in‐loop and out‐of‐loop waters in assisting HNS/HSN proton transfer isomerizations: Bridging vs. surrounding effect

In this work, a density function theory (DFT) study is presented for the HNS/HSN isomerization assisted by 1–4 water molecules on the singlet state potential energy surface (PES). Two modes are considered to model the catalytic effect of these water molecules: (i) water molecule(s) participate directly in forming a proton transfer loop with HNS/HSN species, and (ii) water molecules are out of loop (referred to as out‐of‐loop waters) to assist the proton transfer. In the first mode, for the monohydration mechanism, the heat of reaction is 21.55 kcal · mol^?1 at the B3LYP/6‐311++G** level. The corresponding forward/backward barrier lowerings are obtained as 24.41/24.32 kcal · mol^?1 compared with the no‐water‐assisting isomerization barrier T (65.52/43.87 kcal · mol^?1). But when adding one water molecule on the HNS, there is another special proton‐transfer isomerization pathway with a transition state 10T′ in which the water is out of the proton transfer loop. The corresponding forward/backward barriers are 65.89/65.89 kcal · mol^?1. Clearly, this process is more difficult to follow than the R–T–P process. For the two‐water‐assisting mechanism, the heat of reaction is 19.61 kcal · mol^?1, and the forward/backward barriers are 32.27/12.66 kcal · mol^?1, decreased by 33.25/31.21 kcal · mol^?1 compared with T. For trihydration and tetrahydration, the forward/backward barriers decrease as 32.00/12.60 (30T) and 37.38/17.26 (40T) kcal · mol^?1, and the heat of reaction decreases by 19.39 and 19.23 kcal · mol^?1, compared with T, respectively. But, when four water molecules are involved in the reactant loop, the corresponding energy aspects increase compared with those of the trihydration. The forward/backward barriers are increased by 5.38 and 4.66 kcal · mol^?1 than the trihydration situation. In the second mode, the outer‐sphere water effect from the other water molecules directly H‐bonded to the loop is considered. When one to three water molecules attach to the looped water in one‐water in‐loop‐assisting proton transfer isomerization, their effects on the three energies are small, and the deviations are not more than 3 kcal · mol^?1 compared with the original monohydration‐assisting case. When adding one or two water molecules on the dihydration‐assisting mechanism, and increasing one water molecule on the trihydration, the corresponding energies also are not obviously changed. The results indicate that the forward/backward barriers for the three in‐loop water‐assisting case are the lowest, and the surrounding water molecules (out‐of‐loop) yield only a small effect. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006