Changes In Bond Lengths Research Articles

Ultralong C(sp3)–C(sp3) Single Bonds Shortened and Stabilized by London Dispersion

AbstractA carbon–carbon (C–C) single bond longer than 1.7 Å shows unique bond flexibility, even though a C–C single bond is typically rigid and robust. We report here that the bond length of flexible C–C single bonds surrounded by bulky alkyl groups in novel hexaphenylethane-type hydrocarbons might be affected by weak noncovalent interactions, such as London dispersion. Thanks to London dispersion, an ultralong and flexible C–C single bond exhibits an obvious bond contraction. X-ray analyses and Raman spectroscopy provided direct information regarding the bond length and strength, whereas density functional theory calculations explained the bond contraction driven by London dispersion. The change in bond length of an extremely elongated flexible C–C bond would be a good probe for quantifying weak interactions that are usually difficult to detect.

Effect of in-situ oxidation on the phase composition and magnetic properties of Fe3O4: Implications for zinc hydrometallurgy

• Iron precipitates at different oxidation degrees are obtained by H 2 O 2 . • Ms value of Fe 3 O 4 shows a decrease and then recovery with oxidation. • Magnetic properties are affected via a Fe-O bond length-related mechanism. • The “magnetic iron oxides” method is promoted for industrial iron precipitation. Large quantities of hazardous waste are generated in the removal process of iron in zinc hydrometallurgy, which poses a severely permanent threat to the environment. Recently, an innovative magnetite (Fe 3 O 4 ) method for iron precipitation has been proposed. Whereas, the magnetic separation performance and phase composition of Fe 3 O 4 are sensitively disturbed by the oxidizing conditions in the pregnant leach solution from zinc hydrometallurgy. In this work, a series of Fe 3 O 4 samples with different oxidation degrees were in-situ formed. We found that oxidation did not worsen the Fe removal and that all samples have a relatively high iron content (>42.3%). Meanwhile, although the magnetic properties of the samples showed a decrease (from 32.31 to 6.56 emu/g), it could be recovered (10.60 emu/g) by controlling the oxidation to a certain degree. This is correlated with the phase transition of iron oxides as the oxidation degree increase. Furthermore, it is clarified that the mechanism by which the oxidation affects the magnetic properties was the change of Fe-O bond length, as revealed by Raman and Fourier transform infrared spectrometer measurement. This work provides a new strategy for the practical implication of the “magnetic iron” instead of the magnetite precipitation method in zinc hydrometallurgy.

Systematic DFT studies of CO-Tolerance and CO oxidation on Cu-doped Ni surfaces

Nickel-based surfaces have received significant attention as an efficient substrate for electrooxidation. This work studied doped nickel surfaces with Cu atoms to enhance the CO-Tolerance. A comparative study was performed for CO adsorption upon different cleavage facets of pristine and Cu-doped nickel surfaces, whereas the adsorption energy, charge transfer, and density of state for CO were estimated using GGA-RPBE calculation method. Several adsorption probabilities were considered, and the change in adsorption energy and bond lengths were used to explain the CO adsorption mechanism. Otherwise, the density of state was employed to study the 3σ and 1π orbital to demonstrate the adsorption of CO onto the different facets. According to our analysis, the Cu-doped nickel surface showed higher CO tolerance than the pristine nickel surface. Whereas the calculated CO adsorption energies of Cu-doped surfaces have more positive values than the non-doped counterparts. The catalytic ability of pristine and Cu-doped Ni(111) was studied to evaluate the ability of surface poisoning resistance. Thus, oxidation of CO to CO2 was studied using the Eley-Rideal mechanism upon the pristine and Cu-doped surfaces of Ni(100) where the rate-determining step for CO oxidation upon the reported surfaces was estimated as CO + O2* → CO2* + O* by an energy barrier of 1.05 and 0.9 eV for pristine, and Cu-doped Ni (100).

Photoinduced Electron Transfer in Multicomponent Truxene-Quinoxaline Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) can respond to light in a number of interesting ways. Photochromism is observed when a structural change to the framework is induced by the absorption of light, which results in a color change. In this work, we show that introducing quinoxaline ligands to MUF-7 and MUF-77 (MUF = Massey University Framework) produces photochromic MOFs that change color from yellow to red upon the absorption of 405 nm light. This photochromism is observed only when the quinoxaline units are incorporated into the framework and not for the standalone ligands in the solid state. Electron paramagnetic resonance (EPR) spectroscopy shows that organic radicals form upon irradiation of the MOFs. The EPR signal intensities and longevity depend on the precise structural details of the ligand and framework. The photogenerated radicals are stable for long periods in the dark but can be switched back to the diamagnetic state by exposure to visible light. Single-crystal X-ray diffraction analysis reveals bond length changes upon irradiation that are consistent with electron transfer. The multicomponent nature of these frameworks allows the photochromism to emerge by allowing through-space electron transfer, precisely positioning the framework building blocks, and tolerating functional group modifications to the ligands.

Structural, vibrational and electronic properties of some tetrel-bonded complexes of the fluorinated methanes methyl fluoride, difluoromethane and fluoroform: an ab initio study.

A search has been conducted, by means of ab initio molecular orbital theory, for potential tetrel-bonded complexes formed between the fluorinated methanes methyl fluoride, difluoromethane and fluoroform, and the related hydrides ammonia, water, hydrogen fluoride, phosphine, hydrogen sulphide and hydrogen chloride. Eleven such complexes have been identified, six containing CH3F and five CH2F2. The complexes are typically less strongly bound than their hydrogen-bonded counterparts, and the interaction energies vary in a consistent way with the periodic trend of the electron donors. The intermolecular separations and changes of the relevant intramolecular bond lengths, the wavenumber shifts of the critical vibrational modes and the extents of charge transfer correlate, by and large, with the strengths of interaction.

Room-Temperature Ferromagnetism in Cu/Co Co-Doped ZnO Nanoparticles Prepared by the Co-Precipitation Method: For Spintronics Applications

In current work, pure ZnO and Zn0.96–xCu0.04CoxO (0 ≤ x ≤ 0.05) nanoparticles were synthesized by the co-precipitation method. Structural analysis and phase determination of the formed nanoparticles was carried out using X-ray diffraction (XRD) and Williamson–Hall plots. The hexagonal wurtzite structure was manifested by all the samples with divergent microstructures. The change in lattice parameters, bond length, dislocation density, and lattice strain indicates that Cu and Co were successfully incorporated. Average crystallite size was found to be in the range of 32.16–45.42 nm for various doping concentrations. Field emission scanning electron microscopy results exhibited that the surface morphology is an amalgam of spherical-like and hexagon-like structures. Spherical-shaped grains were homogeneous and evenly distributed all over the structure. Fourier transform infrared spectra indicated that the absorption bands were blue-shifted with increasing Co concentration. The UV–visible absorption spectra showed high absorption in the UV region and weak absorption in the visible region. An increase in the energy band gap for the maximum absorption peak was observed from 3.49 eV for ZnO to 3.88 eV for Zn0.91Cu0.04Co0.05O. The Burstein–Moss effect explained the noticed blue shift in absorption spectra and energy band gaps. The vibrating sample magnetometer study revealed the change in the diamagnetic behavior of pure ZnO to the ferromagnetic behavior of the prepared nanoparticles at room temperature for different doping concentrations. In the current study, we have developed the room-temperature ferromagnetism (RTFM) for Cu and Co co-doped ZnO nanoparticles. Since RTFM is the key objective for dilute magnetic semiconductors, therefore it can be served as the desirable expectant for spintronics applications with improved functionalities and device concepts.

Whole-exome sequencing expands the roles of novel mutations of organic anion transporting polypeptide, ATP-binding cassette transporter, and receptor genes in intrahepatic cholestasis of pregnancy.

Background: Intrahepatic cholestasis of pregnancy (ICP) is associated with a high incidence of fetal morbidity and mortality. Therefore, revealing the mechanisms involved in ICP and its association with fetal complications is very important. Methods: Here, we used a whole-exome sequencing (WES) approach to detect novel mutations of organic anion transporting polypeptide (OTAP) genes, ATP-binding cassette transporter (ABC) genes, and receptor genes associated with ICP in 249 individuals and 1,029 local control individuals. Two available tools, SIFT and PolyPhen-2, were used to predict protein damage. Protein structuremodeling and comparison between the reference and modified protein structures were conducted by SWISS-MODEL and Chimera 1.14rc software, respectively. Results: A total of 5,583 mutations were identified in 82 genes related to bile acid transporters and receptors, of which 62 were novel mutations. These novel mutations were absent in the 1,029 control individuals and three databases, including the 1,000 Genome Project (1000G_ALL), Exome Aggregation Consortium (ExAC), and Single-Nucleotide Polymorphism Database (dbSNP). We classified the 62 novel loci into two groups (damaging and probably damaging) according to the results of SIFT and PolyPhen-2. Out of the 62 novel mutations, 24 were detected in the damaging group. Of these, five novel possibly pathogenic variants were identified that were located in known functional genes, including ABCB4 (Ile377Asn), ABCB11 (Ala588Pro), ABCC2 (Ile681Lys and Met688Thr), and NR1H4 (Tyr149Ter). Moreover, compared to the wild-type protein structure, ABCC2 Ile681Lys and Met688Thr protein structures showed a slight change in the chemical bond lengths of ATP-ligand binding amino acid side chains. The combined 32 clinical data points indicate that the mutation group had a significantly (p = 0.04) lower level of Cl ions than the wild-type group. Particularly, patients with the 24 novel mutations had higher average values of alanine transaminase (ALT), aspartate transaminase (AST), alkaline phosphatase (ALP), total bile acids (TBA), high-density lipoprotein (HDL), and low-density lipoprotein (LDL) than patients with the 38 novel mutations in the probably damaging group and the local control individuals. Conclusion: The present study provides new insights into the genetic architecture of ICP involving these novel mutations.

Short- and Long-Range Cation Disorder in (AgxCu1–x)2ZnSnSe4 Kesterites

Understanding the nature of and controlling the cation disorder in kesterite-based absorber materials remain a crucial challenge for improving their photovoltaic (PV) performances. Herein, the combination of neutron diffraction and synchrotron-based X-ray absorption techniques was implemented to investigate the relationships among cation disorder, defect concentration, overall long-range crystallographic order, and local atomic-scale structure for (AgxCu1–x)2ZnSnSe4 (ACZTSe) material. The joint Rietveld refinement technique was used to directly reveal the effect of cation substitution and quantify the concentration of defects in Ag-alloyed stoichiometric and nonstoichiometric Cu2ZnSnSe4 (CZTSe). The results showed that 10%-Ag-alloyed nonstoichiometric ACZTSe had the lowest concentration of detrimental antisite CuZn defects (∼8 × 1019 defects per cm–3), which was two times lower than pristine and five times lower than the stoichiometric compositions. Moreover, Ag incorporation maintained the concentrations of beneficial Cu vacancies (VCu) and antisite ZnCu defects to >2 × 1020 defects per cm–3. X-ray absorption measurements were performed to verify the degree of disorder through the changes in bond length and coordination number. Therefore, the incorporation of Ag into the CZTSe lattice could control the distribution of antisite defects, in the form of short- and long-range site disorder. This study paves the way to systematically understand and further improve the properties of kesterite-based materials for different energy applications.

Geometric quantum adiabatic methods for quantum chemistry

Quantum algorithms have been successfully applied in quantum chemistry to obtain the ground-state energy of small molecules. Although accurate near the equilibrium geometry, the results can become unreliable when the chemical bonds are broken at large distances. For any adiabatic approach, this is usually caused by serious issues, such as energy gap closing or level crossing along the adiabatic evolution path. In this work, we propose a quantum algorithm based on adiabatic evolution to obtain molecular eigenstates and eigenenergies in quantum chemistry, which exploits a smooth geometric deformation by continuously varying bond lengths and bond angles. We demonstrate its utility in several examples on a noiseless quantum simulator, including ${\mathrm{H}}_{2}\mathrm{O}, {\mathrm{CH}}_{2}$, and a chemical reaction of ${\mathrm{H}}_{2}+{\mathrm{D}}_{2}\ensuremath{\rightarrow}$ 2HD, by uniformly stretching chemical bonds. We find that this new algorithm solves the problems related to energy gap closing and level crossing along the adiabatic evolution path at large atomic distances. The new method performs more stably and achieves better accuracy than our previous adiabatic method [Yu and Wei, Phys. Rev. Research 3, 013104 (2021)]. Furthermore, our fidelity analysis demonstrates that even with finite bond length changes, our algorithm still achieves high fidelity for the ground state.

(Digital Presentation) New Advances and 24/7 Accessibility in Battery Research- Bringing Synchrotron X-Ray Techniques to Your Lab

Rechargeable battery research often involves improving electrodes to electrolyte materials with new chemistry with the end goals to lower cost, extend cycle life, higher energy densities and better safety. Advancements in battery and fuel cell research require the understanding of the complex interplay of several components and factors in a battery ecosystem. It calls for an integrated and multimodality approach involving several new analytical techniques which have to be capable of probing the batteries electrochemistry, structures and composition at different length and time scales, several of which have to be performed non destructively (ex-situ, in situ and in operando). Because of the need to study these in operando or at higher resolution or sensitivity, conventional lab based x-ray techniques are often inadequate. Most of this research is currently performed through synchrotron X-ray techniques. These include: X-ray Absorption Spectroscopy (XAS) to probe changes in oxidation states, bond lengths and coordination numbers of electrochemistry during charge-discharge cycles. XAS comprise XANES (X-ray absorption near edge spectroscopy) & EXAFS (Extended X-ray Absorption Fine Structure). They provide information on element-specific changes in oxidation state and local atomic structure. Such microscopic descriptors are crucial for elucidating charge transfer and structural changes associated with bonding or site mixing, two key factors in evaluating state of charge and modes of cell failure or catalytic efficiency. Another major technique is synchrotron X-ray Imaging at multiple lengthscales, from micrometers to 10s of nanometers through 3D X-ray Microscopy (XRM) to determine structural changes and degradation over time of the complex system, from the electrodes, separators, current collectors to binders. Trace level elemental composition at the ppm or sub-ppm level can be studied through high sensitivity synchrotron X-ray fluorescence spectroscopy (s-XRF)- to track the migration of metallic ions from cathode to anode during charge-discharge cycle or to investigate cross contamination during manufacturing.Unfortunately, many of these X-ray techniques such as XAS has to be performed almost exclusively at synchrotron X-ray light sources, where beamtime is infrequent and experiment time-frames are limited. As a consequence, high level battery, fuel cell or catalyst research in many research institutions have been largely curtailed. In this talk, we will discuss the advancements made in high flux, tunable lab x-ray sources and high efficiency optics for enabling novel synchrotron-equivalent XAS, XRM and XRF techniques in the laboratory. Breakthrough correlative applications through these suite of tools in the field of battery research and catalysts are now feasible in your own laboratory 24/7, without the constraint of limited access nor the research continuity challenges at synchrotron beamlines. Measurements results (including in operando) will be illustrated for conventional NMC batteries to novel solid-state lithium air batteries and next generation battery materials.

Revealing boron adsorption on the α-Ti(0001) surface by first-principles calculations

ABSTRACT In this work, the first-principles calculations were performed to discuss adsorption energies, electronic structures, and phase diagrams of boron atoms adsorbed on a α-Ti(0001) surface at different adsorption sites. The adsorption energy, charge transfer, and density of states of the most stable adsorption site were compared and analyzed. As the coverage increases, the adsorption energy and work function increase. After B adsorption, the internal bond length changes significantly, indicating that B adsorption on the α-Ti(0001) surface belongs to chemical adsorption. The density of states and electron density difference confirm that the interaction between B and Ti strengthens with the increase of coverage. These results provide a theoretical basis for the in-depth understanding of the reaction mechanism of B on the α-Ti(0001) surface.

Ultrafast dynamics of adenine following XUV ionization

The dynamics of biologically relevant molecules exposed to ionizing radiation contains many facets and spans several orders of magnitude in time and energy. In the extreme ultraviolet (XUV) spectral range, multi-electronic phenomena and bands of correlated states with inner-valence holes must be accounted for in addition to a plethora of vibrational modes and available dissociation channels. The ability to track changes in charge density and bond length during ultrafast reactions is an important endeavor toward more general abilities to simulate and control photochemical processes, possibly inspired by those that have evolved biologically. By using attosecond XUV pulses extending up to 35 eV and few-femtosecond near-infrared pulses, we have previously time-resolved correlated electronic dynamics and charge migration occurring in the biologically relevant molecule adenine after XUV-induced sudden ionization. Here, using additional experimental data, we comprehensively report on both electronic and vibrational dynamics of this nucleobase in an energy range little explored to date with high temporal resolution. The time-dependent yields of parent and fragment ions in the mass spectra are analyzed to extract exponential time constants and oscillation periods. Together with time-dependent density functional theory and ab-initio Green’s function methods, we identify different vibrational and electronic processes. Beyond providing further insights into the XUV-induced dynamics of an important nucleobase, our work demonstrates that yields of specific dissociation outcomes can be influenced by sufficiently well-timed ultrashort pulses, therefore providing a new route for the control of the multi-electronic and dissociative dynamics of a DNA building block.

Improved volume variable cluster model method for crystal-lattice optimization: effect on isotope fractionation factor

The isotopic fractionation factor and element partition coefficient can be calculated only after the geometric optimization of the molecular clusters is completed. Optimization directly affects the accuracy of some parameters, such as the average bond length, molecular volume, harmonic vibrational frequency, and other thermodynamic parameters. Here, we used the improved volume variable cluster model (VVCM) method to optimize the molecular clusters of a typical oxide, quartz. We documented the average bond length and relative volume change. Finally, we extracted the harmonic vibrational frequencies and calculated the equilibrium fractionation factor of the silicon and oxygen isotopes. Given its performance in geometrical optimization and isotope fractionation factor calculation, we further applied the improved VVCM method to calculate isotope equilibrium fractionation factors of Cd and Zn between the hydroxide (Zn–Al layered double hydroxide), carbonate (cadmium-containing calcite) and their aqueous solutions under superficial conditions. We summarized a detailed procedure and used it to re-evaluate published theoretical results for cadmium-containing hydroxyapatite, emphasizing the relative volume change for all clusters and confirming the optimal point charge arrangement (PCA). The results showed that the average bond length and isotope fractionation factor are consistent with those published in previous studies, and the relative volume changes are considerably lower than the results calculated using the periodic boundary method. Specifically, the average Si–O bond length of quartz was 1.63 Å, and the relative volume change of quartz centered on silicon atoms was − 0.39%. The average Zn–O bond length in the Zn–Al-layered double hydroxide was 2.10 Å, with a relative volume change of 1.96%. Cadmium-containing calcite had an average Cd–O bond length of 2.28 Å, with a relative volume change of 0.45%. At 298 K, the equilibrium fractionation factors between quartz, Zn–Al-layered double hydroxide, cadmium-containing calcite, and their corresponding aqueous solutions were Delta ^{30/28} {text{Si}}_{{{text{Qtz-H}}_{4} {text{SiO}}_{4} }} = 2.20{permil} , Delta^{18/16} {text{O}}_{ {text{Qtz}}{-} ( {text{H}}_{2} {text{O}} )_{text{n}}} = 36.05{permil}, Delta^{66/64} {text{Zn}}_{ {text{Zn}} {-} {text{Al LDH-Zn}} ( {text{H}}_{2} {text{O}} )_{text{n}}^{2+}} = 1.12{permil} and Delta^{114/110} {text{Cd}}_{ {text{(Cd--Cal)-Cd}} ( {text{H}}_{2} {text{O}} )_ {text{n}}^{2 +} } = - 0.26{permil} respectively. These results strongly support the reliability of the improved VVCM method for geometric optimization of molecular clusters.

Boron Impurity Deposition on a Si(100) Surface in a SiHCl3-BCl3-H2 System for Electronic-Grade Polysilicon Production

A study of boron impurities deposited on a Si(100) surface in a SiHCl3-BCl3-H2 system is reported in this paper, using periodic density functional theory with generalized gradient approximation (GGA). The results show that the discrete distances of BCl3 and SiHCl3 from the surface of the Si(100) unit cell are 1.873 Å and 2.340 Å, respectively, and the separation energies are −35.2549 kcal/mol and −10.64 kcal/mol, respectively. BCl3 and SiHCl3 are mainly adsorbed on the surface of the Si(100) unit cell in particular molecular orientations: the positive position and the hydrogen bottom-two-front position from the analysis of the bond length change and adsorption energy. The adsorption of SiHCl3 and BCl3 is accompanied by a charge transfer from the molecule to the surface of the unit cell of 0.24 and 0.29 eV, respectively. BCl3 reacts more readily than SiHCl3 with the Si(100) surface, resulting in the deposition of boron impurities on the polysilicon surface.

A Smart Molecule Showing Spin Crossover Responsive Aggregation-Induced Emission

A Smart Molecule Showing Spin Crossover Responsive Aggregation-Induced Emission

The deformation of short-range order leading to rearrangement of topological network structure in zeolitic imidazolate framework glasses

SummaryIn recent years, the study of the glassy structure of zeolitic imidazolate frameworks (ZIFs) has been a key breakthrough in glass science. Yet the theoretical understanding of the structure of these complex materials is still in its infancy, especially the short-range structure. The short-structural disorder of two ZIFs and their corresponding molten structure, namely, ZIF-4 and ZIF-62 are studied, using ab initio simulations. Changes in short-range order are investigated, particularly the changes in bond length, bond angle, and tetrahedral unit volume. Furthermore, the asymmetric distribution of organic groups caused by the benzimidazole functional group leads to the difference in short-range disorder between ZIF-4 and ZIF-62 glasses, which contribute to the glass-forming ability difference.

Nonlinear deformation and elasticity of BCC refractory metals and alloys

Application of isotropic pressure or uniaxial strain alters the elastic properties of materials; sufficiently large strains can drive structural transformations. Linear elasticity describes stability against infinitesimal strains, while nonlinear elasticity describes the response to finite deformations. It was previously shown that uniaxial strain along [100] drives refractory metals and alloys towards mechanical instabilities. These include an extensional instability, and a symmetry-breaking orthorhombic distortion caused by a Jahn-Teller-Peierls instability that splays the cubic lattice vectors. Here we analyze these transitions in depth. Eigenvalues and eigenvectors of the Wallace tensor identify and classify linear instabilities in the presence of strain. We show that both instabilities are discontinuous, leading to discrete jumps in the lattice parameters. We provide physical intuition for the instabilities by analyzing the changes in first-principles energy, stress, bond lengths, and angles upon application of strain. Electronic band structure calculations show differential occupation of bonding and antibonding orbitals, driven by the changing bond lengths and leading to the structural transformations. Strain thresholds for these instabilities depend on the valence electron count.

New insights into the excited state intramolecular proton transfer (ESIPT) competition mechanism for different intramolecular hydrogen bonds of Kaempferol and Quercetin in solution

In this work, the process of the Excited State Intramolecular Proton Transfer (ESIPT) competition of Kaempferol and Quercetin in methanol was studied by means of the Density Functional Theory (DFT) and the Time-Dependent Density Functional Theory (TDDFT) method. Two different ESIPT reaction pathways were analyzed by the variation trend of the 3D potential energy surfaces (PESs) with the change of the intramolecular hydroxyl bond length through the PESs of the two molecules of the ground state (S0) and the first excited (S1) state. The ESIPT process only occurred between O25–H28 and O22–H28 and was completed within 33.1fs by molecular excited state dynamics simulation. It is demonstrated that when there are two kinds of hydrogen bonds in the molecule, the ESIPT prefers the six-membered ring hydrogen bonds to the five-membered ring hydrogen bonds.

BF3–Catalyzed Diels–Alder Reaction between Butadiene and Methyl Acrylate in Aqueous Solution—An URVA and Local Vibrational Mode Study

In this study we investigate the Diels–Alder reaction between methyl acrylate and butadiene, which is catalyzed by BF3 Lewis acid in explicit water solution, using URVA and Local Mode Analysis as major tools complemented with NBO, electron density and ring puckering analyses. We considered four different starting orientations of methyl acrylate and butadiene, which led to 16 DA reactions in total. In order to isolate the catalytic effects of the BF3 catalyst and those of the water environment and exploring how these effects are synchronized, we systematically compared the non-catalyzed reaction in gas phase and aqueous solution with the catalyzed reaction in gas phase and aqueous solution. Gas phase studies were performed at the B3LYP/6-311+G(2d,p) level of theory and studies in aqueous solution were performed utilizing a QM/MM approach at the B3LYP/6-311+G(2d,p)/AMBER level of theory. The URVA results revealed reaction path curvature profiles with an overall similar pattern for all 16 reactions showing the same sequence of CC single bond formation for all of them. In contrast to the parent DA reaction with symmetric substrates causing a synchronous bond formation process, here, first the new CC single bond on the CH2 side of methyl acrylate is formed followed by the CC bond at the ester side. As for the parent DA reaction, both bond formation events occur after the TS, i.e., they do not contribute to the energy barrier. What determines the barrier is the preparation process for CC bond formation, including the approach diene and dienophile, CC bond length changes and, in particular, rehybridization of the carbon atoms involved in the formation of the cyclohexene ring. This process is modified by both the BF3 catalyst and the water environment, where both work in a hand-in-hand fashion leading to the lowest energy barrier of 9.06 kcal/mol found for the catalyzed reaction R1 in aqueous solution compared to the highest energy barrier of 20.68 kcal/mol found for the non-catalyzed reaction R1 in the gas phase. The major effect of the BF3 catalyst is the increased mutual polarization and the increased charge transfer between methyl acrylate and butadiene, facilitating the approach of diene and dienophile and the pyramidalization of the CC atoms involved in the ring formation, which leads to a lowering of the activation energy. The catalytic effect of water solution is threefold. The polar environment leads also to increased polarization and charge transfer between the reacting species, similar as in the case of the BF3 catalyst, although to a smaller extend. More important is the formation of hydrogen bonds with the reaction complex, which are stronger for the TS than for the reactant, thus stabilizing the TS which leads to a further reduction of the activation energy. As shown by the ring puckering analysis, the third effect of water is space confinement of the reacting partners, conserving the boat form of the six-member ring from the entrance to the exit reaction channel. In summary, URVA combined with LMA has led to a clearer picture on how both BF3 catalyst and aqueous environment in a synchronized effort lower the reaction barrier. These new insights will serve to further fine-tune the DA reaction of methyl acrylate and butadiene and DA reactions in general.

Hyperconjugative Interactions of the Carbon-Halogen Bond that Influence the Geometry of Cyclic α-Haloacetals.

The analysis of the structures of low-energy conformers of different α-haloacetals reveals changes in bond lengths and geometries that correspond to stabilizing orbital interactions that contribute to the ground-state structures of these systems. Several factors, including the electron-donating and electron-accepting abilities of the substituents on the ring, affect the degree of the electronic interactions in these carbohydrate-like systems. The presence of an α-halogen atom that can participate in hyperconjugation has been shown to contribute to the structural characteristics of the low-energy conformer. The experimental evidence is supported by natural bond order (NBO) analysis to identify the types of interactions and to assess their relative importance.