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A previously developed spectrometer for broadband electron paramagnetic resonance (EPR) spectroscopy of dilute randomly oriented systems has been considerably modified to extend the frequency reach down to the hundred MHz range and to boost concentration sensitivity by 1 to 2 orders of magnitude. The instrument is now suitable for the study of biological systems in particular metalloproteins. As a proof of concept, examples from the class of low-spin ferric hemoproteins are studied in terms of frequency-dependent changes in their EPR spectra. Mono-heme cytochrome c EPR is determined by g-strain over a wide frequency range, whereas a combination of unresolved ligand hyperfine interaction and concentration-dependent intermolecular dipolar interaction becomes dominant at very low frequencies. In the four heme containing cytochrome c3, g-strain combines with intramolecular dipolar interaction over the full-studied frequency range of 0.23-12.0 GHz. It is concluded that the point-dipole approach is inappropriate to describe magnetic interactions between low-spin ferric heme systems and that a body of literature on redox interactions in multi-heme proteins will be affected by this conclusion.

Directional internal rotation in molecular systems, generally controlled by chirality, is known to occur in natural and artificial systems driven by light or fueled chemically, but spontaneous directional molecular rotation is believed to be forbidden. We have designed a molecular rotor, whereby ferrocene and triptycene linked by a methylene bridge provide two rotational degrees of freedom. On the basis of experimental observations, in conjunction with computational data, we show that the two different modes of rotation are strongly coupled and the spatial orientation of the bistable ferrocene moiety controls the barrier to its own rotation about the triptycene axis. It is proposed that the barrier to clockwise 120° rotation across each individual triptycene blade is lower in the M-enantiomer and for counterclockwise 120° rotation, it is lower in its P-counterpart. These findings demonstrate the possibility of locally preferred thermal directional intramolecular rotation for each dynamically interconverting enantiomer.

Independently of the preparation method, for cluster cations of aliphatic amino acids, the protonated form MnH+ is always the dominant species. This is a surprising fact considering that in the gas phase, they dissociate primarily by the loss of 45 Da, i.e., the loss of the carboxylic group. In the present study, we explore the dissociation dynamics of small valine cluster cations Mn+ and their protonated counterparts MnH+ via collision-induced dissociation experiments and ab initio calculations with the aim to elucidate the formation of MnH+-type cations from amino acid clusters. For the first time, we report the preparation of valine cluster cations Mn+ in laboratory conditions, using a technique of cluster ion assembly inside He droplets. We show that the Mn+ cations cooled down to He droplet temperature can dissociate to form both Mn-1H+ and [Mn-COOH]+ ions. With increasing internal energy, the Mn-1H+ formation channel becomes dominant. Mn-1H+ ions then fragment nearly exclusively by monomer loss, describing the high abundance of protonated clusters in the mass spectra of amino acid clusters.

The Waddington mechanism, or the Waddington-type reaction pathway, is crucial for low-temperature oxidation of both alkenes and alcohols. In this study, the Waddington mechanism in the oxidation chemistry of butene and butanol isomers was systematically investigated. Fundamental quantum chemical calculations were conducted for the rate constants and thermodynamic properties of the reactions and species in this mechanism. Calculations were performed using two different ab initio solvers: Gaussian 09 and Orca 4.0.0, and two different kinetic solvers: PAPR and MultiWell, comprehensively. Temperature- and pressure-dependent rate constants were performed based on the transition state theory, associated with the Rice Ramsperger Kassel Marcus and master equation theories. Temperature-dependent thermochemistry (enthalpies of formation, entropy, and heat capacity) of all major species was also conducted, based on the statistical thermodynamics. Of the two types of reaction, dissociation reactions were significantly faster than isomerization reactions, while the rate constants of both reactions converged toward higher temperatures. In comparison, between two ab initio solvers, the barrier height difference among all isomerization and dissociation reactions was about 2 and 0.5 kcal/mol, respectively, resulting in less than 50%, and a factor of 2-10 differences for the predicted rate coefficients of the two reaction types, respectively. Comparing the two kinetic solvers, the rate constants of the isomerization reactions showed less than a 32% difference, while the rate of one dissociation reaction (P1 ↔ WDT12) exhibited 1-2 orders of magnitude discrepancy. Compared with results from the literature, both reaction rate coefficients (R4 and R5 reaction systems) and species' thermochemistry (all closed shell molecules and open shell radicals R4 and R5) showed good agreement with the corresponding values obtained from the literature. All calculated results can be directly used for the chemical kinetic model development of butene and butanol isomer oxidation.

We present the first experimental study of the frontier orbitals in an ultrathin film of the novel hexa-carbene photosensitizer [Fe(btz)3]3+, where btz is 3,3′-dimethyl-1,1′-bis(p-tolyl)-4,4′-bis(1,2,3-triazol-5-ylidene). Resonant photoelectron spectroscopy (RPES) was used to probe the electronic structure of films where the molecular and oxidative integrities had been confirmed with optical and X-ray spectroscopies. In combination with density functional theory calculations, RPES measurements provided direct and site-selective information about localization and interactions of occupied and unoccupied molecular orbitals. Fe 2p, N 1s, and C 1s measurements selectively probed the metal, carbene, and side-group contributions revealing strong metal–ligand orbital mixing of the frontier orbitals. This helps explain the remarkable photophysical properties of iron-carbenes in terms of unconventional electronic structure properties and favorable metal–ligand bonding interactions—important for the continued development of these type of complexes toward light-harvesting and light-emitting applications.

Polycyclic hydrocarbons are often used to understand the electronic structure of nanographene systems. Among them, indeno[1,2b]fluorene and indeno[1,2c]fluorene isomers present a central p-quinodimethane unit leading to unique optical properties. In this work, we characterized the absorption spectra of indeno[1,2b]fluorene and [2,1-c]diindeno[n]thiophene derivatives with (spin-flip) simplified time-dependent density functional theory [(SF-)sTD-DFT] methods. Note that the SF-sTD-DFT level of theory allows a computationally efficient treatment for large diradicals. To interpret spectra, we implemented natural transition orbitals (NTOs) at both SF-sTD-DFT and sTD-DFT levels. This compact and method-independent representation of the electronic excitation provides a simple interpretation for the low-lying excited states of this set of molecules in terms of three different types of NTOs: "quinoid", "aromatic", and "π-bonded". When comparing with experiment, we found that only one molecule of this set is actually a high-spin triplet diradical. Others are almost closed-shell molecules with a very small contribution from a doubly excited configuration that only the spin-flip method could capture. The small amount of static correlation recovered by the spin-flip active space provides a linear relation between the first visible theoretical and experimental excitation energies among this set.

The reactions of 1-tetradecene and 1-pentadecene, the C14 and C15 linear 1-alkenes, with OH radicals in the presence of NOx were investigated in a series of environmental chamber experiments. Particle-phase β-hydroxynitrates, dihydroxynitrates, dihydroxycarbonyls, and 1,4-hydroxynitrates and gas-phase aldehydes were sampled and then identified and quantified using a suite of offline analytical techniques that included derivatization, gas and liquid chromatography, and multiple types of mass spectrometry. Measured molar yields of products formed by OH radical addition to the C═C double bond, including β-hydroxynitrates, dihydroxynitrates, dihydroxycarbonyls (which have not been previously directly quantified with high accuracy), and aldehydes were 0.125 ± 0.01, 0.048 ± 0.005, 0.240 ± 0.04, and 0.268 ± 0.03 (0.264 ± 0.02 and 0.271 ± 0.04 for the formaldehyde and tridecanal/tetradecanal co-products of β-hydroxyalkoxy radical decomposition), respectively. These values give a total molar yield of 0.681 ± 0.05, which agrees very well with the results of kinetics measurements that indicate that the fraction of reaction that occurs by OH radical addition is 0.70. The yields were used to calculate branching ratios for all OH radical addition pathways, including a value of 0.18 for the formation of dihydroxynitrates from the reaction of dihydroxyperoxy radicals with NO and values of 0.47 and 0.53 for β-hydroxyalkoxy radical decomposition and isomerization. The results were used with literature data on the yields of aldehydes measured for similar reactions of smaller alkenes, a model for the effect of carbon number on branching ratios for organic nitrate formation, and a mechanism for H atom abstraction derived from studies of linear alkanes to achieve a complete, quantitative gas-phase reaction mechanism for 1-alkenes. The results should also be useful for constructing mechanisms for more complex reactions of volatile organic compounds.

Light-induced blinking, an inherent feature of many forms of super-resolution microscopy, has been linked to transient reduction of the fluorescent cyanine dye used as an imaging agent. There is, however, only scant literature information related to one-electron reduced cyanine dyes, especially in an aqueous environment. Here, we examine a small series of cyanine dyes, possessing disparate π-conjugation lengths, under selective reducing or oxidizing conditions. The experiment allows recording of both differential absorption spectra and decay kinetics of the resultant one-electron reduced or oxidized transient species in water. Relative to the ground state, absorption transitions for the various radicals are weak and somewhat broadened but do allow correlation with the π-conjugation length. In all cases, absorption maxima lie to the blue of the main ground-state transition. Under anaerobic conditions, the transient species decay on the microsecond to millisecond time scale, with the mean lifetime depending on molecular structure, radiation dose, and dye concentration. The experimental absorption spectra recorded for the one-electron reduced radicals and the presumed dimer cation radical compare well to spectra obtained from time-dependent density functional theory calculations. The results allow conclusions to be drawn regarding the plausibility of the reduced species being responsible for light-induced blinking in direct stochastic optical reconstruction microscopy.

The gas-phase rotational spectrum of (cyanomethylene)cyclopropane, (CH2)2C═CHCN, generated by a Wittig reaction between the hemiketal of cyclopropanone and (cyanomethylene)triphenylphosphorane, is presented for the first time. This small, highly polar nitrile is a cyclopropyl-containing structural isomer of pyridine. The rotational spectra of the ground state and two vibrationally excited states were observed, analyzed, and least-squares fit from 130 to 360 GHz. Over 3900 R-, P-, and Q-branch, ground-state rotational transitions were fit to low-error, partial octic, A- and S-reduced Hamiltonians, providing precise determinations of the spectroscopic constants. The two lowest-energy vibrationally excited states, ν17 and ν27, form a Coriolis-coupled dyad displaying small a- and b-type resonances. Transitions for these two states were measured and least-squares fit to a two-state, partial octic, A-reduced Hamiltonian in the Ir representation with nine Coriolis-coupling terms (Ga, GaJ, GaK, GaJJ, Fbc, FbcJ, FbcK, Gb, and GbJ). The observation of many resonant transitions and nine nominal interstate transitions enabled a very accurate and precise energy difference between ν17 and ν27 to be determined: ΔE17,27 = 29.8975453 (33) cm-1. The spectroscopic constants presented herein provide the foundation for future astronomical searches for (cyanomethylene)cyclopropane.

Ceria (CeO2) is a well-known catalytic oxide with many environmental, energy production, and industrial applications, most of them involving water as a reactant, byproduct, solvent, or simple spectator. In this work, we parameterized a Ce/O/H ReaxFF for the study of ceria and ceria/water interfaces. The parameters were fitted to an ab initio training set obtained at the DFT/PBE0 level, including the structures, cohesive energies, and elastic properties of the crystalline phases Ce, CeO2, and Ce2O3; the O-defective structures and energies of vacancy formation on CeO2 bulk and CeO2 (111) surface, as well as the absorption and reaction energies of H2 and H2O molecules on CeO2 (111). The new potential reproduced reasonably well all the fitted properties as well as the relative stabilities of the different ceria surfaces, the oxygen vacancies formation, and the energies and structures of associative and dissociative water molecules on them. Molecular dynamics simulations of the liquid water on the CeO2 (111) and CeO2 (100) surfaces were carried out to study the coverage and the mechanism of water dissociation. After equilibration, on average, 35% of surface sites of CeO2 (111) are hydroxylated whereas 15% of them are saturated with molecular water associatively adsorbed. As for the CeO2 (100) surface, we observed that water preferentially dissociates covering 90% of the available surface sites in excellent agreement with recent experimental findings.

The thermal unimolecular decomposition of 2-methyltetrahydrofuran (2-MTHF) was studied behind reflected shock waves in a single-pulse shock tube over the temperature range of 1179-1361 K and pressure range of 9-17 atm. Methane, ethylene, ethane, 1,3-butadiene, propylene, acetaldehyde, and acetylene were identified as products in the decomposition of 2-MTHF. A reaction scheme was proposed to explain the mechanism for the observed products. The experimentally determined rate coefficients were best fit to an Arrhenius expression for the overall decomposition and is represented as ktotalexp(1179-1361 K) = (3.23 ± 0.59) × 1011 s-1 exp(-51.3 ± 1.4 kcal mol-1/RT). Quantum chemistry methods were used to calculate the energetics and kinetics of various possible unimolecular dissociation pathways involved in the thermal decomposition of 2-MTHF. The initial decomposition of 2-MTHF occurs predominantly via ring-methyl (C-CH3) single bond fission, leading to the formation of tetrahydrofuran (C4H7O) radical, and methyl radical was found to be the major reaction compared to all the possible initial bond fission, ring opening, and molecular elimination channels. The temperature-dependent rate coefficients for the unimolecular dissociation of 2-MTHF were calculated using the RRKM (Rice-Ramsperger-Kassel-Marcus) theory in combination with the CCSD(T)/cc-pVTZ//B3LYP/cc-pVTZ level of electronic structure calculations over the temperature range of 800-1500 K. The computed high-pressure limiting rate coefficients for the initial decomposition of 2-MTHF through C-CH3 single bond fission channel were found to be ∼2 times higher in the temperatures between 800 and 900 K, and above this temperature, they agree well with the values reported in the literature.

The ultraviolet (UV) photodissociation dynamics of the jet-cooled cyclohexyl (c-C6H11) radical is studied using the high-n Rydberg atom time-of-flight (HRTOF) technique. The cyclohexyl radical is produced by the 193 nm photodissociation of chlorocyclohexane and bromocyclohexane and is examined in the photolysis wavelength region of 232-262 nm. The H-atom photofragment yield (PFY) spectrum contains a broad peak centered at 250 nm, which is in good agreement with the UV absorption spectrum of the cyclohexyl radical and assigned to the 3p Rydberg states. The translational energy distributions of the H-atom loss product channel, P(ET)'s, are bimodal, with a slow (low ET) component peaking at ∼6 to 7 kcal/mol and a fast (high ET) component peaking at ∼44-48 kcal/mol. The fraction of the average translational energy in the total excess energy, ⟨fT⟩, is in the range of 0.16-0.25 in the photolysis wavelength region of 232-262 nm. The H-atom product angular distribution of the slow component is isotropic, while that of the fast component is anisotropic with an anisotropy parameter of β ≈ 0.5-0.7. The bimodal product translational energy and angular distributions indicate two dissociation pathways to the H + C6H10 products in cyclohexyl. The high-ET anisotropic component is from a repulsive, prompt dissociation on a repulsive potential energy surface coupling with the Rydberg excited states to produce H + cyclohexene. The low-ET isotropic component is consistent with the unimolecular dissociation of hot radical on the ground electronic state after internal conversion from the Rydberg states. The similarity of the photodissociation dynamics of the cyclohexyl radical to the previously studied small linear and branched alkyls expands on the understanding of the dissociation dynamics of alkyl radicals to include larger cyclic alkyl radicals.

Pyrrole-2-carbaldehyde (Pa) forms one of the unnatural nucleic acid bases, and as a base pair with 7-(2-thienyl)imidazo[4,5-b]pyridine (Ds), it has been known to be stable in DNA. The Ds-Pa pair is stabilized in DNA via van der Waals' interaction and shape fitting. There are some studies on the origin of its stability and reactivity in the ground state. However, for a successful unnatural base pair, it needs to be stable not only in the ground state but also upon irradiation with UV-visible light. To understand the photoinduced reactivity, we investigate the excited-state properties of the Pa base and understand the energetically feasible photoprocesses that can occur upon excitation in the UV region. Two distinct pathways are obtained. One of the pathways involves an out-of-plane mode and has some similarities with the deactivation channels in the natural pyrimidine bases. On the other hand, the second pathway involves an excited-state proton transfer.

The energetics of small cationic tantalum clusters and their gas-phase adsorption and dehydrogenation reaction pathways with methane are investigated with ion-trap experiments and spin-density-functional-theory calculations. Tan+ clusters are exposed to methane under multicollision conditions in a cryogenic ring electrode ion-trap. The cluster size affects the reaction efficiency and the number of consecutively dehydrogenated methane molecules. Small clusters (n = 1-4) dehydrogenate CH4 and concurrently eliminate H2, while larger clusters (n > 4) demonstrate only molecular adsorption of methane. Unique behavior is found for the Ta+ cation, which dehydrogenates consecutively up to four CH4 molecules and is predicted theoretically to promote formation of a [Ta(CH2-CH2-CH2)(CH2)]+ product, exhibiting C-C coupled groups. Underlying mechanisms, including reaction-enhancing couplings between potential energy surfaces of different spin-multiplicities, are uncovered.

The complex formed from trimethylamine ((CH3)3N) and trifluoromethanesulfonic acid (triflic acid, CF3SO3H) has been observed by Fourier transform microwave spectroscopy in a supersonic jet. Spectroscopic data, most notably 14N nuclear quadrupole coupling constants, are combined with computational results at several levels of theory to unambiguously demonstrate complete or near-complete proton transfer from the triflic acid to the trimethylamine upon complexation. Thus, the system is best regarded as a trimethylammonium triflate ion pair in the gas phase. The formation of an isolated ion pair in a 1:1 complex of a Bronsted acid and base is unusual and likely arises due to the strong acidity of triflic acid. Simple energetic arguments based on proton affinities and the Coulomb interaction energy can be used to rationalize this result.

Formates are a class of organic molecules emitted into the atmosphere from fuel additives and industrial solvents. Formate-derived esters can undergo a vast range of chemical reactions in the atmosphere, most of which are initiated by oxidation by hydroxyl radicals. One potential reaction upon their interaction with atmospheric water is proton transfer to form protonated formates. The goal of the present work is to explore the dissociation of these protonated species and thus their possible atmospheric fate. Tandem mass spectrometry was employed to study the unimolecular dissociation of the protonated forms of methyl- (1), ethyl- (2), isopropyl- (3), tert-butyl- (4), and phenylformate (5). 1 and 2 lose CO as a common fragmentation product, forming a protonated alcohol, and 2 also generates neutral ethanol (forming protonated CO). 3 and 4 readily lose the stable isopropyl and tert-butyl radicals as well as neutral alkenes propene and isobutene. Methanol loss is also observed from both ions. 5 exhibits both phenyl radical loss (similar to 3 and 4) and CO loss (like 1 and 2). Density functional theory was used to explore the observed minimum energy reaction pathways for each ion, and CBS-QB3 single-point energy calculations provided reliable energetics.

It is well known that the presence of an electron-withdrawing substituent (EWS) placed near the halogen (X) atom on a Lewis acid molecule amplifies the ability of this unit to engage in a halogen bond with a base. Quantum calculations are applied to examine how quickly these effects fade as the EWS is moved further and further from the X atom. Conjugated alkene and alkyne chains of varying lengths with a terminal C-I first facilitate analysis as to how the number of these multiple bonds affects the strength of CI··N XB to NH3. Then, electron-withdrawing F and C≡N substituents are placed on the opposite end of the chain, and their effects on the XB properties are monitored as a function of their distance from I. These same EWSs are added to the ortho, meta, and para positions of aromatic iodobenzene. It is found that the XB grows in strength as more triple bonds are added to the alkyne, but there is little change caused by elongating an alkene. The cyano group has a much stronger effect than does F. While F strengthens the XB, its effects are quickly attenuated as it is moved further from I. The consequences of C≡N substitution are stronger and extend over a longer distance. Placement of an EWS on the phenyl ring diminishes with distance: o > m > p, and the effects of disubstitution are nearly additive. These trends apply not only to energetics but also to geometries, properties of the wave function, σ-hole depth, and NMR shielding.

We demonstrate that 2,4-bis(4,5-diphenyl-1H-imidazol-2-yl)phenol (2,4-bImP) undergoes photoinduced conversion into the so-called "π-conjugated zwitterion" after causing an excited-state intramolecular proton transfer (ESIPT) reaction. The powder sample of 2,4-bImP exhibits largely Stokes-shifted fluorescence characteristics to ESIPT fluorophores. On the other hand, its originally colorless solutions become colored when exposed to UV light for several minutes, whose color depends on the type of solvent. In particular, the CHCl3 solution rapidly turns dark green with the absorption maximum around 700 nm, and the colored solution is nearly restored to original by alternating addition of acid and base. To explain such drastic and reversible color changes, we hypothesized that the occurrence of ESIPT (i.e., deprotonation of the phenol and protonation of the imidazolyl group at its 2-position) triggered the charge-separated structure between the negatively charged phenolate and the positively charged imidazoliumyl group at its 4-position, which allowed resonance with the neutral p-quinoid structure. The formation of this π-conjugated zwitterion was strongly supported by the results of 1H and 15N NMR and Raman measurements.

Density functional theory (DFT) calculations were conducted to gain insight into the reaction mechanism of the Bronsted acid-catalyzed unsymmetrical 1,2,4,5-tetrazine synthesis. Various possible reaction pathways were considered, and the most favorable one can be characterized via sequential six steps, including addition of DCM to hydrazine 1 giving complex IM4, N-H bond activation in IM4 mediated by sulfur, AcOH-assisted substitution of 3 with sulfur-activated hydrazine 2, HNO2-assisted addition of nitrile to intermediate 8, cyclization, and intramolecular elimination leading to the final product 7. Among the six steps, sulfur activation of IM4 N-H bond is found to be the rate-determining step (RDS). The mechanism rationalizes the experimental observation that 2 equiv of sulfur leads to the best yield of product. Furthermore, we disclosed that the Bronsted acid additives (i.e., acetic acid and nitrous acid) served triple roles as catalyst, proton shuttle, and hydrogen bond donor and acceptor in the whole catalysis.

The predissociation thresholds of the early transition metal boride diatomics (MB, M = Sc, Ti, V, Y, Zr, Nb, La, Hf, Ta, W) have been measured using resonant two-photon ionization (R2PI) spectroscopy, allowing for a precise assignment of the bond dissociation energy (BDE). No previous experimental measurements of the BDE exist in the literature for these species. Owing to the high density of electronic states arising from the ground and low-lying separated atom limits in these open d-subshell species, a congested spectrum of vibronic transitions is observed as the energy of the ground separated atom limit is approached. Nonadiabatic and spin-orbit interactions among these states, however, provide a pathway for rapid predissociation as soon as the ground separated atom limit is reached, leading to a sharp decrease in signal to background levels when this limit is reached. Accordingly, the BDEs of the early transition metal borides have been assigned as D0(ScB) 1.72(6) eV, D0(TiB) 1.956(16) eV, D0(VB) 2.150(16) eV, D0(YB) 2.057(3) eV, D0(ZrB) 2.573(5) eV, D0(NbB) 2.989(12) eV, D0(LaB) 2.086(18) eV, D0(HfB) 2.593(3) eV, D0(TaB) 2.700(3) eV, and D0(WB) 2.730(4) eV. Additional insight into the chemical bonding and electronic structures of these species has been achieved by quantum chemical calculations.

The regioselectivity in the 1,3-dipolar cycloaddition (1,3-DC) between five-membered cyclic nitrone and methylenecyclopropane (MCP) has been studied through density functional theory (DFT) calculations. The computational study of 1,3-DC with different 1-alkyl- (or 1,1-dialkyl)-substituted alkenes and the comparison with MCP have evidenced that the electrostatic interaction has a central role in the regioselectivity of the reactions. It has been observed that the electronic effect of the substituent (donor or attractor groups) determines the polarization of the alkene double bond and the reaction mechanism, consequently determining the interaction with nitrones and favoring an orientation between this moiety and the dipolarophile.

The thermodynamic properties and band gap energies were evaluated for six ortho- and peri-fused polycyclic aromatic hydrocarbons (PAHs): triphenylene; benzo[a]pyrene; benzo[e]pyrene; perylene; benz...

We analyzed the interactions present in complexes that acetone, azomethane, dimethylamine, dimethyl ether, methyl acetate, and oxirane form with 39 different (H2O)n clusters (n = 1-10). A random generation of configurations and a subsequent screening procedure were employed to sample representative interactions. Using quantum chemical computations, we calculated the associated binding energies, which range from -0.19 to -10.76 kcal/mol at the DLPNO-CCSD(T)/CBS level. It was found that the binding energies can be understood in terms of various factors, including the water cluster size, the nature of the organic molecule, and the type of hydrogen bond donor. We find that the most stable complexes often arise from a combination of a strong hydrogen bond plus a secondary interaction between the organic molecule and the water cluster.

The bistability of molecular switches is an essential characteristic in their use as functional components in molecular-based devices and machines. For photoswitches, light-driven switching between two stable states proceeds via short-lived changes of the bond order in electronically excited states. Here, bistable switching of a ditertbutyl-substituted spiropyran photoswitch is instead demonstrated by oxidation and subsequent reduction in an overall four-state cycle. The spiropyran structure chosen has reduced sensitivity to the effect of secondary electrochemical processes such as H+ production and provides transient access to a decreased thermal Z-E isomerization barrier in the one electron oxidized state, akin to that achieved in the corresponding photochemical path. Thus, we show that the energy needed for switching spiropyrans to the merocyanine form on demand, typically delivered by a photon, can instead be provided electrochemically. This opens up further opportunities for the utilization of spiropyrans in electrically controlled applications and devices.

The effect of pressure on the structural reorganization of ferrocene, Fc = (C5H5)2Fe, is studied using density functional theory (DFT) calculations assisted by evolutionary crystal structure prediction algorithms based on USPEX code. Pressure brings the individual molecules in close contact, and above 220 GPa, the 18-electron closed-shell molecular unit undergoes polymerization through the formation of quasi-one-dimensional (1D) chains, [(C5H5)2Fe]∞, termed as polyferrocene (p-Fc). Pressure induced polymerization (PIP) of Fc causes significant deviations from the 5-fold symmetry of the cyclopentadiene (Cp, C5H5 rings) and loss of planarity due to the onset of envelope-like distortions. This triggers distortions within the multidecker sandwich structures and σ(C-C) bond formation between the otherwise weak noncovalently interacting Cp rings in Fc crystals. Pressure gradually reduces the band gap of Fc, and for p-Fc, metallic states are found due to increased electronic coupling between the covalently linked Cp rings. Polyferrocene is significantly more rigid than ferrocene as evident from the 5-fold increase in its bulk modulus. Pressure dependent Raman spectra show a clear onset of polymerization in Fc at P = 220 GPa. Higher mechanical strength coupled with its metallicity makes p-Fc an interesting candidate for high pressure synthesis.

Charge separation and intersystem crossing play critical roles in various applications of organic long persistent luminescence materials, including light-emitting diodes, chemical sensors, theranostics, and many biomedical and information applications. Using first-principles calculations, we demonstrate that an azobenzene acting as a photoswitch can be used for altering the configuration of a donor-switch-acceptor (D-S-A) molecular system to ensure charge separation and promote intersystem crossing upon photoexcitation. The trans to cis photoisomerization of an azobenzene switch creates an electron trap that stabilizes the charge-separated state. The cis conformation further facilitates the singlet to triplet intersystem crossing in the excited state. Our theoretical study of the D-S-A system may help the design of long persistent luminescent organic devices.

This study investigates the fluorescence quenching mechanism of formaldehyde detection probe Naph1 and its contrast probe Naph3 in water samples and discussed the effect of the electron-donating group and electron-withdrawing group on fluorescence characteristics based on density functional theory (DFT) and time-dependent density functional theory (TD-DFT). We optimized the structures of the four probes Naph1, Naph1-S, Naph3, and Naph3-S (Scheme 1) and calculated the absorption and emission spectra, which were in good agreement with the experiment. Frontier molecular orbitals (FMOs) were used to analyze the charge arrangement in the excited state. To investigate the intramolecular proton transfer (ESIPT) phenomenon, a potential energy curve was constructed. The amount of fragment charge transfer was analyzed by the IFCT method, and then it was determined whether there was an intramolecular charge transfer (ICT) process. It was found that there was an ICT process in Naph3. The electronic effect of the functional groups did not determine the ICT characteristics and the fluorescence characteristics of the substance. Furthermore, the spin-orbit coupling (SOC) constant based on the intersystem crossing (ISC) was supplemented, which showed that the fluorescence quenching of Naph1 and Naph3 was caused by the ISC and the corresponding quenching of Naph3-S was caused by charge transfer (CT) in the excited state.

The vibrationally resolved absorption spectra and exciton dynamics in the α-zinc phthalocyanine aggregates are theoretically investigated by using a non-Markovian stochastic Schrodinger equation. The model Hamiltonian adopted for spectral and dynamic simulations explicitly includes the couplings for both nearest-neighbor and remote exciton transfer, and it is parametrized from first-principles calculations. The results indicate that aggregation lengths and remote exciton transfer significantly influence the relative energy alignment between delocalized Frenkel exciton (FE) and charge transfer (CT) states, which in turn strongly affects the relative intensities of the two absorption peaks in the Q-band region. Analytical formulas are derived to establish quantitative structure-spectra relationships in aggregates, and they offer simple patterns to extract electronic-state properties directly from absorption spectra. The dynamics simulations reveal that the light absorption can directly generate mixed states with both FE and CT features, but it is hard for the photoexcitation from the Q-band region to generate free carriers due to the high energies of charge-separated states.

The ubiquitous role of water and its amphiprotic nature call for a deeper insight into the physical-chemical properties of hydrogen-bonded complexes formed with building blocks of biomolecules. In this work, the semiexperimental (SE) approach combined with the template model (TM) protocol allowed the accurate determination of the equilibrium structure of two isomeric forms of the imidazole-water complex. In this procedure, the integration of experiment (thanks to a recent rotational spectroscopy investigation) and theory is exploited, also providing the means of assessing the reliability and accuracy of different quantum-chemical approaches. Overall, this study demonstrated the robustness of the combined SE-TM approach, which can provide accurate results using affordable quantum-chemical methods. Finally, the structural and energetic characteristics of these complexes have been examined in detail and compared with those of analogous heterocycle-water adducts, also exploiting energy decomposition analyses.

The exhaustive exploration of the potential energy surfaces of CE2M2 (E = Si-Pb, M = Li, and Na) revealed seven global minima containing a planar tetracoordinate carbon (ptC). The design was based on a π-localization strategy, resulting in a ptC embedded in a linear or a bent allene-type E=C=E motif. The magnetic response showed a σ-aromaticity in the bent E=C=E fragments. The bonding analysis indicated that the ptCs form C-E covalent bonds and C-M electrostatic interactions.

We studied the thermal decomposition of dimethyl carbonate (DMC, C3H6O3) in a flash vacuum pyrolysis reactor in the 1100-1700 K range. The reaction products and intermediates were probed by vacuum ultraviolet synchrotron radiation in a photoelectron photoion coincidence (PEPICO) spectrometer to record isomer-specific photoion mass-selected threshold photoelectron (ms-TPE) spectra. Reaction pathways were explored using quantum chemical calculations, which confirmed the experimental observation that the intramolecular migration of a methyl group, yielding dimethyl ether (DME, C2H6O) and carbon dioxide, dominates the initial unimolecular decomposition chemistry. The role of a second potentially important channel, namely, C-O bond fission to yield methyl radicals, could not be determined experimentally due to the short lifetime of the ·C2H3O3 radical and overlapping sequential decomposition products. However, potential energy surface and microcanonical rate constant calculations predict 2 to 3 orders of magnitude lower rates for this channel than for decarboxylation to yield DME. Consequently, DMC pyrolysis shows bewilderingly similar products and product abundances as DME pyrolysis. This coincides with DMC combustion modeling studies, which found that DME is a key intermediate in the mechanism. Furthermore, we have detected traces of methyl formate and formaldehyde, produced after the hydrogen shift to the central carbon atom in DMC. Ethylene and acetylene could be established as bimolecular reaction products because their abundance depended strongly on the DMC concentration. It is intriguing to compare the decomposition of DMC with that of the structurally similar methylal (dimethoxymethane, DMM). While methanol and formaldehyde are produced in similar quantities in DMM, thanks to low-energy hydrogen-transfer reactions, the methanol channel is almost fully suppressed in DMC due to the absence of hydrogens at the central carbon atom and the thermodynamically favored decarboxylation. These new mechanistic insights may help the development of predictive combustion models for fuel additives and biofuels.

Different substituents and benzene ring numbers had significant effects on the fluorescence phenomenon of 2-aryloxazoline derivatives as observed in an experiment. Here, we select five 2-aryloxazoline derivatives with different substituents and benzene ring numbers (2u, 2ad, 2af, 2ai, and 2ah) to analyze the effects on the fluorescence phenomena. For 2ad, 2ah, and 2ai, first, the geometric structures are optimized based on the density functional theory and time-dependent density functional theory methods. The analysis of the obtained bond parameters reveals the variation of hydrogen bond interactions from S0 to S1 states. Second, the calculated absorption and emission spectra are consistent with the experimental values, which proves that the theoretical method is feasible. Finally, through the analysis of the infrared vibrational spectrum, reduced density gradient isosurfaces, frontier molecular orbitals, and potential energy curves, the strengthening mechanism of the hydrogen bond interaction and the ability of the excited-state intramolecular proton transfer (ESIPT) reaction to occur are further explained. Since the proton transfer reactions of 2u and 2af occur spontaneously under photoexcitation, they have no stable structures in the S1 state. In conclusion, due to the different substituents, 2u is more prone to the proton transfer reaction than 2ad. For 2af, 2ai, and 2ah with different benzene ring numbers, the ESIPT reaction is more difficult to occur as the number of benzene rings increases. The ability of the ESIPT reaction to occur follows the order 2af → 2ah → 2ai. For 2-aryloxazoline derivatives with different substituents or different benzene ring numbers, the hydrogen bond strengthening mechanism has been authenticated, which promotes the occurrence of the ESIPT reactions.

High-resolution photoelectron (PE) spectra of liquid methanol and ethanol were measured using a liquid microjet and He IIα radiation (40.813 eV). The vertical ionization energy and the ionization threshold were determined as 9.70 ± 0.07 and 8.69 ± 0.07 eV for methanol and 9.52 ± 0.07 and 8.52 ± 0.07 eV for ethanol, respectively. Individual photoemission bands observed for the liquids are well correlated with those in PE spectra of the gaseous samples also measured in the present study, except that the liquid band positions were shifted on average by −1.23 eV for methanol and −1.10 eV for ethanol as compared to the gas. The 5a′ and 7a′ bands of liquid methanol exhibit specifically larger broadening than other bands, for which we attempted spectral fitting with two components, similarly with the case of the 3a1 band of liquid water. PE spectra of both liquid and gaseous ethanol are congested partly due to the presence of the trans and gauche isomers; however, the overall band positions are generally in good agreement with predictions based on quantum chemical calculations. Comparison of the measured PE spectra with experimental and simulated X-ray emission spectra indicate that spectral differences in the lowest ionization band of both methanol and ethanol originate from involvement of nuclear dynamics in the X-ray emission process.

The structural properties and nonbonding interactions of a menthol-based deep eutectic solvent (DES) were investigated in detail employing experimental and computational methods. A mass spectrometry analysis confirmed the formation of 1:1 l-menthol/acetic acid. A molecular dynamics simulation was used to figure out energetically most favorable cluster conformers of the 1:1 l-menthol/acetic acid system. Density functional theory at the ωB97XD/6-311G (d,p) level of theory was employed to optimize the isolated structures and to calculate their thermochemical properties. Both experimental and computed IR spectra were analyzed for the samples. Additionally, vibrational circular dichroism (VCD) spectra of the samples were measured to prove the chirality transfer. Principal component analysis (PCA) was used to make the data interpretation more vivid. All the spectral data analyses and nanostructure elucidation proved the spontaneous formation of the DES through the formation of strong hydrogen bonding. Experimental solvatochromism and computed highest occupied molecular orbital-lowest unoccupied molecular orbital gaps validated the reasoning. Moreover, comparative VCD and IR spectral analyses clearly indicated a chirality transfer from the chiral menthol to achiral acetic acid. This study suggests that various techniques, such as mass spectrometry, IR, solvatochromism, and computed IR-VCD could be useful and important tools to elucidate nanostructure and nonbonding interactions of a DES. VCD could be used as an excellent complementary technique to IR spectroscopy for a chiral molecule-based DESs.

The ability of density functional theory (DFT) and time-dependent DFT (TDDFT) methods for the accurate prediction of the energies and oscillator strengths of the excited states in a series of fully conjugated meso-meso β-β β-β triple-linked porphyrin oligomers (porphyrin tapes 2-12) was probed in the gas phase and solution using several exchange-correlation functionals. It was demonstrated that the use of the hybrid B3LYP functional provides a good compromise for the accurate prediction of the localized π-π* and intramolecular charge-transfer transitions, thus allowing confident interpretation of the UV-vis-NIR spectra of porphyrin oligomers. The TDDFT-based sum-over-state (SOS) calculations for the porphyrin tape dimer 2 and trimer 3 as well as parent monomer 1 correctly predicted the signs and shapes of the magnetic circular dichroism (MCD) signals in the low-energy region of the spectra.

Structural studies of ammonium halide nanoparticles can help to reveal fundamental information about the detailed nature of intermolecular forces. This study focuses on small ammonium fluoride clusters, which exhibit complex behavior in comparison to other ammonium halide clusters due to the weak acidity and strong hydrogen-bonding ability of HF. Calculations of optimized structures and binding energies are presented for cation, anion, and neutral clusters using MP2, CCSD(T), FNO-CCSD(T), ωB97M-V, and MN15 methods. The extent to which proton transfer occurs between two given cluster components was quantified using a dimensionless proton-transfer parameter (ξ

The triplet-triplet annihilation (TTA) effect of sensitizers themselves can lead to the additional quenching of lifetimes of triplet states; therefore, how to weaken the TTA effect of sensitizers is an urgent issue to be resolved for their further applications. Besides, it remains a tremendous challenge for constructing supramolecular systems of photosensitizers based on photosensitizer-functionalized pillararenes because there have been very few investigations on them. Thus, 2,6-diiodo-1,3,5,7-tetramethyl-8-phenyl-4,4-difluoroboradiazaindacene (DIBDP) and ethoxy pillar[5]arene (EtP5) were utilized to synthesize a DIBDP-functionalized pillar[5]arene (EtP5-DIBDP), a cyano-containing DIBDP (G) used as a guest molecule was also prepared, and they were used to investigate the electron-transfer mechanism between EtP5 and DIBDP moieties and weaken the TTA effect of DIBDP moieties. The theoretical computational results of frontier molecular orbitals and isosurfaces of spin density preliminarily predicted that the cavities of the EtP5 moiety had influence on the fluorescence emission of DIBDP units but not on their triplet states in EtP5-DIBDP. The fluorescence emission intensities in a variety of solvents with different polarities and electrochemical studies revealed that there was electron transfer from EtP5 to the DIBDP units, and the electron-transfer process had influence on the fluorescence emission but not on the triplet states of DIBDP moieties in EtP5-DIBDP, which verified the results of density functional theory calculations. The triplet state lifetimes of EtP5-DIBDP were longer than those of DIBDP and G and the photooxidation abilities of EtP5-DIBDP were better than those of DIBDP and G at a high concentration (1.0 × 10-5 M) in various solvents; in contrast, the intrinsic triplet state lifetimes and singlet oxygen quantum yields (ΦΔ) of DIBDP, G, and EtP5-DIBDP were very similar. This was because the steric hindrance of EtP5 moieties could weaken the TTA effect of DIBDP moieties without influencing their intrinsic triplet state lifetimes in EtP5-DIBDP.

Grignard reagents are commonly used in organic synthesis, yet their ability to form stable anionic states has not been recognized thus far. In this work, representative examples of RMgF, RMgCl, and RMgBr molecules involving methyl, ethyl, and phenyl functional groups serving as R substituents are investigated regarding their equilibrium structures, adiabatic electron affinities, and vertical electron detachment energies of their daughter anions. The electronic stabilities determined for the negatively charged Grignard compounds are then compared to those predicted for their corresponding magnesium halides. The anions formed by RMgX (R = Me, Et, Ph; X = F, Cl, Br) molecules are found to be adiabatically electronically stable valence-bound systems characterized by relatively large vertical electron detachment energies spanning the 0.79-1.62 eV range. In addition, significant structural relaxation upon attachment of an excess electron is predicted for all Grignard compounds considered. Furthermore, the re-examination of the anions formed by magnesium halides resulted in recognizing them as valence-bound rather than dipole-bound anions, in contrast to the earlier interpretations.

The pyrolysis of chlorobenzene (C6H5Cl) at 760 Torr was studied in the temperature range of 873–1223 K. The pyrolysis products including intermediates and chlorinated aromatics were detected and qu...

Methyl salicylate (MS) as a subunit of larger salicylates found in commercial sunscreens has been shown to exhibit keto-enol tautomerization and dual fluorescence emission via excited-state intramolecular proton transfer (ESIPT) after the absorption of ultraviolet (UV) radiation. However, its excited-state relaxation mechanism is unclear. Herein, we have employed the quantum mechanics(CASPT2//CASSCF)/molecular mechanics method to explore the ESIPT and excited-state relaxation mechanism of MS in the lowest three electronic states, that is, S

Two-photon absorption (TPA) enables the excitation of molecules by comparatively lower energy photons with longer penetration depth and higher spatial precision control, which advances the uses of organic molecules in various applications. In this work, we report two simple all-organic molecules C

We develop a methodology for calculating, analyzing and visualizing nuclear magnetic shielding densities, which are calculated from the current density via the Biot-Savart relation. Atomic contributions to nuclear magnetic shielding constants can be estimated within our framework with a Becke partitioning scheme. The new features have been implemented in the GIMIC program and are applied in this work to the study of the $^1$H and $^{13}$C nuclear magnetic shieldings in benzene (C$_6$H$_6$) and cyclobutadiene (C$_4$H$_4$). The new methodology allows a visual inspection of the spatial origins of the positive (shielding) and negative (deshielding) contributions to the nuclear magnetic shielding constant of a single nucleus, something which has not been hitherto easily accomplished. Analysis of the shielding densities shows that diatropic and paratropic current-density fluxes yield both shielding as well as deshielding contributions, as the shielding or deshielding is determined by the direction of the current-density flux with respect to the studied nucleus instead of the tropicity. Becke partitioning of the magnetic shieldings shows that the magnetic shielding contributions mainly originate from the studied atom and its nearest neighbors, confirming the localized character of nuclear magnetic shieldings., 18 pages, 8 figures, includes supporting information

As the first thermal stable molecule with a B≡B bond, the diboryne complex protected by N-heterocyclic carbene ligands (NHC-B≡B-NHC) has attracted much interest. Researchers point out that π-back-donation highly stabilizes the B≡B bond besides σ-donation, both of which are induced by NHC ligands. In this work, details of the π-back-donation are revisited by using DFT calculations. There are two delocalized π* orbitals in NHC, and the symmetry of one π* orbital is highly adaptive to the π orbitals in B≡B bond, whereas the other cannot be involved in the π-back-donation. In staggered configuration, two orthogonal π orbitals of B≡B interact with this π* orbital in each NHC ligand, respectively, to form π-back-donations in both sides. This interaction has proven to be more intensive than π-conjunction, resulting in the lower energy of the staggered isomer compared with the eclipsed one containing greater π-conjunction. Moreover, intensity of the π-back-donation can be enhanced by reducing the energy levels of the matched π* orbitals in ligands, which gives references for the design of stable diborynes.

Diethyl carbonate (DEC) oxidation with different levels of O3 addition was performed in an atmospheric laminar flow reactor from 400 to 850 K. Experimental results showed that, without O3 addition,...

The photodissociation dynamics of methyl formate in the electronic ground state S0, initiated by a 248 nm-wavelength laser, is studied by direct dynamics simulations. We analyze five channels, wher...

Adsorption of polymers from an aqueous solution onto clay minerals is of great interest to many applications such as water purification and soil conditioning. Molecular dynamics simulations were performed to study the adsorption of anionic polyacrylamide (APAM) on anionic montmorillonite, in an aqueous solution containing monovalent or divalent salts. Compared with monovalent salts (NaCl), the enhancement of APAM adsorption brought by divalent salts (CaCl

In a specifically designed molecular structure, two sp2-hybridized carbon atoms align their unhybridized 2pz orbitals in the same orientation to form an extremely long C2pz-C2pz σ-single bond that goes beyond 3 A in length. This new type of C-C σ-bond (coined as a fringe bond) can be made more than 1 A longer than the current experimental world record (∼1.8 A) and 300 kJ/mol weaker than the ordinary C-C σ-bond (∼330 kJ/mol). If such molecular monomers are polymerized into infinite chains, the extended long C-C saturated σ-bonding framework manifests band gaps similar to those of some conventional iconic organic-conducting polymers based on conjugated networks of unsaturated bonds.

Relativistic density functional theory has been employed to characterize [AnO2(L)]0/-1 complexes, where An = U, Np, Pu, and Am, and L is the recently reported hexa-aza porphyrin analogue, termed dipyriamethyrin, which contains six nitrogen donor atoms (four pyrrolic and two pyridine rings). Shorter axial (An═O) and longer equatorial (An-N) bond lengths are observed when going from AnVI to AnV. The actinide to pyrrole nitrogen bonds are shorter as compared to the bonds to the pyridine nitrogens; the former also play a dominant role in the formation of the actinyl (VI and V) complexes. Natural population analysis shows that the pyrrole nitrogen atoms in all the complexes carry higher negative charges than the pyridine nitrogens. Upon binding actinyl ions with the ligand a significant ligand-to-metal charge transfer takes place in all the actinyl (VI and V) complexes. The formation energy of the actinyl(VI,V) complexes in the gas-phase is found to decrease in the order of UO2L > PuO2L > NpO2L > AmO2L. This trend is consistent with results for the formation of complexes in dichloromethane solution. The calculated ΔG and ΔH values are negative for all the complexes. Energy decomposition analysis (EDA) indicates that the interactions between actinyl(V/VI) and ligand are mainly controlled by electrostatic components over covalent orbital interactions, and the covalent character gradually decreases from U to Am for both pentavalent and hexavalent actinyl complexes.

The dissociative photoionization of methyl vinyl ketone (MVK), an important intermediate in the atmospheric oxidation of isoprene, has been studied by photoelectron photoion coincidence spectroscopy. In the photon energy range of 9.5-13.8 eV, four main fragment ions were detected at m/z 55, 43, 42, and 27 aside from the parent ion at m/z 70. The m/z 55 fragment ion (C2H3CO+) is formed from ionized MVK by direct methyl loss, while breaking the C-C bond on the other side of the carbonyl group results in the acetyl cation (CH3CO+, m/z 43) and the vinyl radical. The m/z 42 fragment ion is formed via a CO-loss from the molecular ion after a methyl shift. The lightest fragment ion, the vinyl cation (C2H3+ at m/z 27), is produced in two different reactions: acetyl radical loss from the molecular ion and CO-loss from C2H3CO+. Their contributions to the m/z 27 signal are quantified based on the acetyl and vinyl fragment thermochemical anchors and quantum chemical calculations. Based on the experimentally derived appearance energy of the m/z 43 fragment ion, a new, experimentally derived heat of formation is proposed herein for gaseous methyl vinyl ketone (ΔfH0K = -94.3 ± 4.8 kJ mol-1; ΔfH298K = -110.5 ± 4.8 kJ mol-1), together with cationic heats of formation and bond dissociation energies.

The electronic and magnetic properties of the ligand-decorated Fe6S8 cluster and fused superatomic dimer are investigated using first-principles density functional theory. It is shown that the redox properties of the Fe6S8 cluster can be effectively controlled by altering the nature of the attached ligands. Donor ligands such as phosphines reduce the ionization energy of the Fe6S8 cluster, whereas the acceptor ligands such as CO increase the electron affinity. Such variation in the redox properties of the Fe6S8 cluster is the result of the ligand-induced shift in the cluster's electronic levels, so the occupation number remains mostly unaffected, leading to a marginal change in the spin magnetic moment of the cluster. A combination of two identical Fe6S8 clusters decorated by unbalanced ligands results in a superatomic dimer with a massive dipole moment and a large spin magnetic moment. Donor ligands on one side of the superatomic dimer with acceptor ligands on the other cause significant intercluster charge transfer. The resulting superatomic dimer offers an interesting motif for spintronics-related applications.