Bioinspired benzimidazole-phenol constructs with an intramolecular hydrogen bond connecting the phenol and the benzimidazole have been synthesized to study both proton-coupled electron transfer (PCET) and excited-state intramolecular proton transfer (ESIPT) processes. Strategic incorporation of a methyl group disrupts the coplanarity between the aromatic units, causing a pronounced twist, weakening the intramolecular hydrogen bond, decreasing the phenol redox potential, reducing the chemical reversibility, and quenching the fluorescence emission. Infrared spectroelectrochemistry and transient absorption spectroscopy confirm the formation of the oxidized product upon PCET and probe excited-state relaxation mechanisms, respectively. Density functional theory calculations of redox potentials corroborate the experimental findings. Additionally, time-dependent density functional theory calculations uncover the fluorescence quenching mechanism, showing that the nonradiative twisted intramolecular charge transfer state responsible for fluorescence quenching is more energetically favorable in the methyl-substituted system. Incorporating groups causing steric hindrance expands the design of biomimetic systems capable of performing both PCET and ESIPT.

A bioinspired naphthoquinone model of the quinones in photosynthetic reaction centers but bearing an intramolecular hydrogen-bonded carboxylic acid has been synthesized and characterized electrochemically, spectroscopically, and computationally to provide mechanistic insight into the role of proton-coupled electron transfer (PCET) of quinone reduction in photosynthesis. The reduction potential of this construct is 370 mV more positive than the unsubstituted naphthoquinone. In addition to the reversible cyclic voltammetry, infrared spectroelectrochemistry confirms that the naphthoquinone/naphthoquinone radical anion couple is fully reversible. Calculated redox potentials agree with the experimental trends arising from the intramolecular hydrogen bond. Molecular electrostatic potentials illustrate the reversible proton transfer driving forces, and analysis of the computed vibrational spectra supports the possibility of a combination of electron transfer and PCET processes. The significance of PCET, reversibility, and redox potential management relevant to the design of artificial photosynthetic assemblies involving PCET processes is discussed.

Cryogenic ion vibrational spectra of D2-tagged cyanobenzoate (CBA) derivatives are obtained and analyzed to characterize the intrinsic spectroscopic responses of the -CO2- headgroup to its location on the ring in both the isolated anions and the cationic complexes with divalent metal ions, M2+ (M = Mg, Ca, Sr). The benzonitrile functionality establishes the different ring isomers (para, meta, ortho) according to the location of the carboxylate and provides an additional reporter on the molecular response to the proximal charge center. The aromatic carboxylates display shifts slightly smaller than those observed for a related aliphatic system upon metal ion complexation. Although the CBA anions display very similar band patterns for all three ring positions, upon complexation with metal ions, the ortho isomer yields dramatically different spectral responses in both the -CO2- moiety and the CN group. This behavior is traced to the emergence of a tridentate binding motif unique to the ortho isomer in which the metal ions bind to both the oxygen atoms of the carboxylate group and the N atom of the cyano group. In that configuration, the -CO2- moiety is oriented perpendicular to the phenyl ring, and the CN stretching fundamental is both strong and red-shifted relative to its behavior in the isolated neutral. The behaviors of the metal-bound ortho complexes occur in contrast to the usual blue shifts associated with "Lewis" type binding of metal ions end-on to -CN. The origins of these spectroscopic features are analyzed with the aid of electronic structure calculations, which also explore differences expected for complexation of monovalent cations to the ortho carboxylate. The resulting insights have implications for understanding the balance between electrostatic and steric interactions at metal binding sites in chemical and biological systems.

Developing cost-effective and efficient catalysts containingnonpreciousmetals is critical for chemical-to-electrical conversion technologies.The onset potentials for the fundamentally important oxygen reductionreaction, oxygen evolution reaction, and hydrogen evolution reactioncan be determined from binding free energies. Herein, artificial neuralnetworks (ANNs) were trained on a dataset of approximately 1500 metal-nitrogen-dopedcarbon (MNC) complexes containing first-row transition metals to predictOOH, O, OH, and H binding free energies from transferable densitymatrix-based features. These ANNs use density matrices from gas-phaseHartree-Fock theory with a minimal basis set for a fixed geometryto predict binding free energies at the level of solution-phase densityfunctional theory (DFT) with a much larger basis set for optimizedgeometries. The ANNs were able to predict binding free energies witha mean absolute error of around 0.1 eV. Several feature selectiontools such as recursive feature elimination were used to decreasethe number of density matrix-based features and increase accuracy.The off-diagonal density matrix elements between the metal and ligatingnitrogens were found to be especially predictive of binding free energies.This machine learning strategy has the potential to facilitate thediscovery of efficient and abundant metal-based catalysts for electrochemicalenergy conversion.

Expanding proton-coupled electron transfer to multiproton translocations (MPCET) provides a bioinspired mechanism to transport protons away from the redox site. This expansion has been accomplished by separating the initial phenolic proton donor from the pyridine-based terminal proton acceptor by a Grotthuss-type proton wire made up of concatenated benzimidazoles that form a hydrogen-bonded network. However, it was found that the midpoint potential of the phenol oxidation that launched the Grotthuss-type proton translocations is a function of the number of benzimidazoles in the hydrogen-bonded network; it becomes less positive (i.e., a weaker oxidant) as the number of bridging benzimidazoles increases. Herein, we report a strategy to maintain the high redox potential necessary for oxidative processes relevant to artificial photosynthesis, e.g., water oxidation and long-range MPCET processes for managing protons. The integrated structural and functional roles of the benzimidazole-based bridge provide sites for substitution of the benzimidazoles with electron-withdrawing groups (e.g., trifluoromethyl groups). Such substitution increases the midpoint potential of the phenoxyl radical/phenol couple so that proton translocations over ∼11 Å become thermodynamically comparable to that of an unsubstituted system where one proton is transferred over ∼2.5 Å. The extended, substituted system maintains the hydrogen-bonded network; infrared spectroelectrochemistry confirms reversible proton translocations from the phenol to the pyridyl terminal proton acceptor upon oxidation and reduction. Theory supports the change in driving force with added electron-withdrawing groups and provides insight into the role of electron density and electrostatic potential in MPCET processes associated with these Grotthuss-type proton translocations.

The utilization of artificial neural networks (ANNs) provides strategies for accelerating molecular simulations. Herein, ANNs are implemented as propagators of the time-dependent Schrödinger equation to simulate the quantum dynamics of systems with time-dependent potentials. These ANN propagators are trained to map nonstationary wavepackets from a given time to a future time within the discrete variable representation. Each propagator is trained for a specified time step, and iterative application of the propagator enables the propagation of wavepackets over long time scales. Such ANN propagators are developed and applied to one- and two-dimensional proton transfer systems, which exhibit nuclear quantum effects such as hydrogen tunneling. These ANN propagators are trained for either a specific time-independent potential or general potentials that can be time-dependent. Hierarchical, multiple time step algorithms enable parallelization, and the extension to higher dimensions is straightforward. This strategy is applicable to quantum dynamical simulations of diverse chemical and biological processes.

Artificial neural networks (ANNs) have become important in quantum chemistry. Herein, applications to nuclear quantum effects, such as zero-point energy, vibrationally excited states, and hydrogen tunneling, are explored. ANNs are used to solve the time-independent Schrödinger equation for single- and double-well potentials representing hydrogen-bonded molecular systems capable of proton transfer. ANN mappings are trained to predict the lowest five proton vibrational energies, wave functions, and densities from the proton potentials and to predict the excited state proton vibrational energies and densities from the proton ground state density. For the inverse problem, ANN mappings are trained to predict the proton potential from the proton vibrational energy levels or the proton ground state density. This latter mapping is theoretically justified by the first Hohenberg-Kohn theorem establishing a one-to-one correspondence between the external potential and the ground state density. ANNs for two- and three-dimensional systems are also presented to illustrate the straightforward extension to higher dimensions.

Proton-coupled electron transfer (PCET) reactions depend on the hydrogen-bond connectivity between sites of proton donors and acceptors. The 2-(2 '-hydroxyphenyl) benzimidazole (BIP) based systems, which mimic the natural Tyr(Z)-His190 pair of Photosystem II, have been useful for understanding the associated PCET process triggered by one-electron oxidation of the phenol. Substitution of the benzimidazole by an appropriate terminal proton acceptor (TPA) group allows for two-proton translocations. However, the prototropic properties of substituted benzimidazole rings and rotation around the bond linking the phenol and the benzimidazole can lead to isomers that interrupt the intramolecular hydrogen-bonded network and thereby prevent a second proton translocation. Herein, a strategic symmetrization of a benzimidazole based system with two identical TPAs yields an uninterrupted network of intramolecular hydrogen bonds regardless of the isomeric form. NMR data confirms the presence of a single isomeric form in the disubstituted system but not in the monosubstituted system in certain solvents. Infrared spectroelectrochemistry demonstrates a two-proton transfer process associated with the oxidation of the phenol occurring at a lower redox potential in the disubstituted system relative to its monosubstituted analogue. Computational studies support these findings and show that the disubstituted system stabilizes the oxidized two-proton transfer product through the formation of a bifurcated hydrogen bond. Considering the prototropic properties of the benzimidazole heterocycle in the context of multiple PCET will improve the next generation of novel, bioinspired constructs built by concatenated units of benzimidazoles, thus allowing proton translocations at nanoscale length.

Electric fields control chemical reactivity in a wide range of systems, including enzymes and electrochemical interfaces. Characterizing the electric fields at electrode-solution interfaces is critical for understanding heterogeneous catalysis and associated energy conversion processes. To address this challenge, recent experiments have probed the response of the nitrile stretching frequency of 4-mercaptobenzonitrile (4-MBN) attached to a gold electrode to changes in the solvent and applied electrode potential. Herein, this system is modeled with periodic density functional theory using a multilayer dielectric continuum treatment of the solvent and at constant applied potentials. The impact of the solvent dielectric constant and the applied electrode potential on the nitrile stretching frequency computed with a grid-based method is in qualitative agreement with the experimental data. In addition, the interfacial electrostatic potentials and electric fields as a function of applied potential were calculated directly with density functional theory. Substantial spatial inhomogeneity of the interfacial electric fields was observed, including oscillations in the region of the molecular probe attached to the electrode. These simulations highlight the microscopic inhomogeneity of the electric fields and the role of molecular polarizability at electrode-solution interfaces, thereby demonstrating the limitations of mean-field models and providing insights relevant to the interpretation of vibrational Stark effect experiments.

The essential role of a well-defined hydrogen-bond network in achieving chemically reversible multiproton translocations triggered by one-electron electrochemical oxidation/reduction is investigated by using pyridylbenzimidazole-phenol models. The two molecular architectures designed for these studies differ with respect to the position of the N atom on the pyridyl ring. In one of the structures, a hydrogen-bond network extends uninterrupted across the molecule from the phenol to the pyridyl group. Experimental and theoretical evidence indicates that an overall chemically reversible two-proton-coupled electron-transfer process (E2PT) takes place upon electrochemical oxidation of the phenol. This E2PT process yields the pyridinium cation and is observed regardless of the cyclic voltammogram scan rate. In contrast, when the hydrogen-bond network is disrupted, as seen in the isomer, at high scan rates (∼1000 mV s-1) a chemically reversible process is observed with an E1/2 characteristic of a one-proton-coupled electron-transfer process (E1PT). At slow cyclic voltammetric scan rates (<1000 mV s-1) oxidation of the phenol results in an overall chemically irreversible two-proton-coupled electron-transfer process in which the second proton-transfer step yields the pyridinium cation detected by infrared spectroelectrochemistry. In this case, we postulate an initial intramolecular proton-coupled electron-transfer step yielding the E1PT product followed by a slow, likely intermolecular chemical step involving a second proton transfer to give the E2PT product. Insights into the electrochemical behavior of these systems are provided by theoretical calculations of the electrostatic potentials and electric fields at the site of the transferring protons for the forward and reverse processes. This work addresses a fundamental design principle for constructing molecular wires where protons are translocated over varied distances by a Grotthuss-type mechanism.

A prescription for sampling isobaric generalized ensembles with molecular dynamics is presented and applied to the generalized replica exchange method (gREM), which was designed to simulate first-order phase transitions. The properties of the isobaric gREM ensemble are discussed, and a study is presented for the liquid-vapor equilibrium of the guest molecules given for gas hydrate formation with the mW water model. Phase diagrams, critical parameters, and a law of corresponding states are obtained.