Proton transfer and solitonic excitations in model one-dimensional hydrogen-bonded systems

The solitonic models of proton transfer in a molecular hydrogen-bonded chain have been examined with respect to the shape of protonic interaction potential. The kink-like excitations with quadratic, quartic, Morse, and Toda interactions are reported and analyzed.     

Double proton transfer and charge transfer transitions in hydrogen-bonded systems: formic acid dimer

The barriers for double proton transfer in the ground and lowest Π-Π^* and Π-Π^* excited states of the formic acid dimer have been calculated within a modified INDO scheme. Analysis of the nature of the excited electronic states, with emphasis on charge-transfer transitions, has been performed. The results indicate a lower barrier in the excited Π-Π^* states than in the ground state.     

Proton transfer in the hydrogen-bonded chains of lepidocrocite: a computational study

A responsible approach to the development of alternative energy sources, storage and conversion systems is to utilize abundant materials, with minimal or no negative environmental impacts. Here we report that lepidocrocite (γ-FeOOH, a naturally occurring metastable phase of iron oxyhydroxide) shows great promise as a proton conductor, based on sophisticated first-principles calculations that include the important corrections of on-site Coulomb interactions for this strongly correlated material. Our results show how proton transfer is facilitated by phonon vibration modes and relatively low transition energy barriers.     

Proton translocation and electronic relaxation along a hydrogen-bonded molecular wire in a 6-hydroxyquinoline/acetic acid complex

A hydrogen-bonded network formed between 6-hydroxyquinoline (6-HQ) and acetic acid (AcOH) has been characterized using a time-resolved fluorescence technique. In the bridged hydrogen-bonded complex of cis-6-HQ and AcOH, an excited-state reaction proceeds via proton transfer along the hydrogen bond, resulting in a keto-tautomer (within approximately 200 ps) that exhibits large Stokes-shifted fluorescence. The unbridged complex also undergoes excited-state proton transfer, but the Stokes shift is rather smaller.     

Proton transfer in small model systems: A density functional study

The structures, interaction energies, and proton-transfer features of some representative intermolecular complexes are determined by using a density functional which incorporates gradient corrections and, as recently suggested by Becke, some Hartree–Fock exchange. The results are compared with those obtained by high-order many-body perturbation theory and by a number of more conventional density functionals. Hydrogen-bond strengths and interatomic distances between heavy atoms are well reproduced by several density functionals. However, inclusion of some Hartree–Fock exchange is mandatory to improve XH bond lengths, and, especially, energy barriers governing proton transfer. Use of the new functional significantly improves the agreement with experimental and post-Hartree–Fock results. This paves the route for a detailed theoretical study of proton-transfer processes in large, biologically significant systems. © 1995 John Wiley & Sons, Inc.     

Ion-ion reactions in the gas phase: Proton transfer reactions of protonated pyridine with multiply charged oligonucleotide anions

Isolated triply and doubly charged anions of the single-stranded deoxynucleotide 5′-d(AAAA)-3′ were allowed to undergo ion-ion proton transfer reactions with protonated pyridine cations within a quadrupole ion trap mass spectrometer. Sufficiently high ion number densities and spatial overlap of the oppositely charged ion clouds could be achieved to yield readily measurable rates. Three general observations were made: (1) the ion-ion reaction rate constants were estimated to be 10^{? (7 ? 8)} cm³ ion^?1 s^?1; (2) the ion-ion reaction rates were found to be dependent on the reactant ion number density, which could be controlled by both the reactant ion number and the pseudopotential well depth, and (3) very little fragmentation, if any, was observed, as might normally be expected with highly exothermic proton transfer reactions.     

Properties of strong hydrogen-bonded systems: The formation of hydrogen-bonded ion pair in amine·HCL systems

The hydrogen-bonded complexes between CH₃NH₂ and (CH₃)₂NH with HCl have been studied by the ab initio molecular orbital method using the 4–31G basis set. Calculations show that the proton potential curve has a single minimum near to the nitrogen atom in both complexes. This means that the proton has been transferred from HCl to the amine. ΔE and the dipole moment of the complexes studied are as follows: ?18.2 kcal mol^?1, 10.3 D for methylamine ·HCl, and ?21.7 kcal mol^?1 11.1 D for the corresponding dimethylamine complex. Other properties of the hydrogen-bonded ion pairs are discussed.     

Proton dissociation and transfer in hydrated phosphoric acid clusters

The dynamics and mechanisms of proton dissociation and transfer in hydrated phosphoric acid (H₃PO₄) clusters under excess proton conditions were studied based on the concept of presolvation using the H₃PO₄–H₃O⁺–nH₂O complexes (n = 1–3) as the model systems and ab initio calculations and Born–Oppenheimer molecular dynamics (BOMD) simulations at the RIMP2/TZVP level as model calculations. The static results showed that the smallest, most stable intermediate complex for proton dissociation (n = 1) is formed in a low local‐dielectric constant environment (e.g., ε = 1), whereas proton transfer from the first to the second hydration shell is driven by fluctuations in the number of water molecules in a high local‐dielectric constant environment (e.g., ε = 78) through the Zundel complex in a linear H‐bond chain (n = 3). The two‐dimensional potential energy surfaces (2D‐PES) of the intermediate complex (n = 1) suggested three characteristic vibrational and ¹H NMR frequencies associated with a proton moving on the oscillatory shuttling and structural diffusion paths, which can be used to monitor the dynamics of proton dissociation in the H‐bond clusters. The BOMD simulations over the temperature range of 298–430 K validated the proposed proton dissociation and transfer mechanisms by showing that good agreement between the theoretical and experimental data can be achieved with the proposed rate‐determining processes. The theoretical results suggest the roles played by the polar solvent and iterate that insights into the dynamics and mechanisms of proton transfer in the protonated H‐bond clusters can be obtained from intermediate complexes provided that an appropriate presolvation model is selected and that all of the important rate‐determining processes are included in the model calculations. © 2015 Wiley Periodicals, Inc.     

Proton transfer in the 1,1-dinitroethane/n-dibutylamine complex

The ¹H NMR spectra of 1,1-dinitroethane/n-dibutylamine solutions in CCl₄ have been investigated. It is shown that two types of complexes, the CH … N hydrogen bond complex and the ion pair are present in the solution simultaneously, with slow exchange through proton transfer between them. The exchange rates, activation energy and enthalpy of proton transfer are determined. It can be concluded that the act of proton transfer from carbon to nitrogen and back is kinetically determined.     

Application of CNDO/II to some hydrogen-bonded systems

Short results are given of the application of the CNDO/II method to hydrogen bonding. Formic acid (monomer and dimer), trifluoroacetic acid and the hydrogen bis(trifluoroacetate)ion were treated.     

Proton relay in a one-dimensional hydrogen-bonded chain composed of water molecules and a squaric acid derivative.

The crystal structure of a hydrated crystal of bis(squaryl)biphenyl (BSQB*4H2O), in which two squaric acid moieties are connected with a 4,4'-biphenyl unit, was characterized by the presence of a one-dimensional hydrogen-bonded chain composed of BSQB and water molecules. X-ray crystallographic analysis showed that BSQB exists in a dianion form and that, on average, two of the four water molecules are protonated. The enhanced temperature dependence of the thermal parameters of the oxygen atoms of the water molecules suggested dynamic disorder of the water molecules. The solid-state magic angle spinning deuterium NMR spectrum of BSQB*4D2O revealed that deuterons are exchanged between heavy water molecules and oxonium ions with an exchange rate of ca. 700 Hz around 250 K and that deuterons start to migrate in a hydrogen-bonded cluster of water molecules. Ac dielectric measurements were also used to examine the dynamic process in the hydrated crystal. The dielectric permittivity of the crystal dramatically increased above 250 K with a distinct frequency dependence (epsilon' = 4.7 x 10(4) at 340 K and 1 kHz). The frequency dependence of tan delta at 290 K exhibited a maximum at 3.0 kHz, and this maximum shifted to lower frequencies when the temperature of the crystal decreased. These experimental results suggested that in the one-dimensional hydrogen-bonded chain of BSQB*4H2O a proton relay between oxonium ions and water molecules occurred within a cluster of four water molecules and that the relay was transmitted to the adjacent cluster mediated by the modulation of the negative charge distribution of the BSQB dianion. These phenomena were interpreted as the solitonic migration of the charged domain boundaries along the one-dimensional hydrogen-bonded chain.     

Concerted proton-electron transfer in the oxidation of hydrogen-bonded phenols

Three phenols with pendant, hydrogen-bonded bases (HOAr-B) have been oxidized in MeCN with various one-electron oxidants. The bases are a primary amine (-CPh(2)NH(2)), an imidazole, and a pyridine. The product of chemical and quasi-reversible electrochemical oxidations in each case is the phenoxyl radical in which the phenolic proton has transferred to the base, (*)OAr-BH(+), a proton-coupled electron transfer (PCET) process. The redox potentials for these oxidations are lower than for other phenols, predominately from the driving force for proton movement. One-electron oxidation of the phenols occurs by a concerted proton-electron transfer (CPET) mechanism, based on thermochemical arguments, isotope effects, and DeltaDeltaG(++)/DeltaDeltaG degrees . The data rule out stepwise paths involving initial electron transfer to form the phenol radical cations [(*)(+)HOAr-B] or initial proton transfer to give the zwitterions [(-)OAr-BH(+)]. The rate constant for heterogeneous electron transfer from HOAr-NH(2) to a platinum electrode has been derived from electrochemical measurements. For oxidations of HOAr-NH(2), the dependence of the solution rate constants on driving force, on temperature, and on the nature of the oxidant, and the correspondence between the homogeneous and heterogeneous rate constants, are all consistent with the application of adiabatic Marcus theory. The CPET reorganization energies, lambda = 23-56 kcal mol(-)(1), are large in comparison with those for electron transfer reactions of aromatic compounds. The reactions are not highly non-adiabatic, based on minimum values of H(rp) derived from the temperature dependence of the rate constants. These are among the first detailed analyses of CPET reactions where the proton and electron move to different sites.     

Photophysics of intramolecularly hydrogen-bonded aromatic systems: ab initio exploration of the excited-state deactivation mechanisms of salicylic acid

Excited state reaction paths and the corresponding energy profiles of salicylic acid have been determined with the CC2 method, which is a simplified version of singles-and-doubles coupled cluster theory. At crucial points of the potential energy hypersurfaces, single-point energy calculations have been performed with the CASPT2 method (second-order perturbation theory based on the complete active space self-consistent field reference). Hydrogen transfer along the intramolecular hydrogen bond as well as torsion and pyramidization of the carboxy group have been identified as the most relevant photochemical reaction coordinates. The keto-type planar S(1) state reached by barrierless intramolecular hydrogen transfer represents a local minimum of the S(1) energy surface, which is separated by a very low barrier from a reaction path leading to a low-lying S(1)-S(0) conical intersection via torsion and pyramidization of the carboxy group. The S(1)-S(0) conical intersection, which occurs for perpendicular geometry of the carboxy group, is a pure biradical. From the conical intersection, a barrierless reaction path steers the system back to the two known minima of the S(0) potential energy surface (rotamer I, rotamer II). A novel structure, 7-oxa-bicyclo[4.2.0]octa-1(6),2,4-triene-8,8-diol, has been identified as a possible transient intermediate in the photophysics of salicylic acid.     

The importance of nanoscopic ordering on the kinetics of photoinduced charge transfer in aggregated pi-conjugated hydrogen-bonded donor-acceptor systems

Aggregated complexes of diaminotriazine oligo(p-phenylene vinylene) (OPV) units hydrogen bonded to different complementary perylene bisimide (PERY) compounds have been investigated by means of absorption, circular dichroism, photoluminescence, and photoinduced absorption spectroscopy. These studies reveal that in the aggregated state an ultrafast photoinduced charge separation occurs via an intermolecular pathway in the J-type stack of hydrogen-bonded OPV-PERY arrays. The subsequent charge recombination reaction strongly depends on small structural differences within the J-type geometry as revealed by comparison of stacked supramolecular dimers, trimers, and covalently OPV-PERY linked systems. A coupled oscillator model is used to analyze absorption and circular dichroism spectra and to identify intermolecular arrangements that are consistent with the experimental spectra and the charge-transfer kinetics.     

A combined quantum chemical/molecular mechanical study of hydrogen-bonded systems

A computational approach, which involves the combination of the OPLS force field and molecular orbital MNDO , AM 1, and PM 3 methods, has been developed to describe the effects of a large, molecular mechanically simulated environment on the Hamiltonian of a quantum chemical system. To test the validity of the combined quantum mechanical/molecular mechanical (QM /MM ) potential, a systematic study of the structures and energies of neutral and charged hydrogen-bonded complexes has been carried out, including comparisons with pure semiempirical calculations and available experimental and ab initio data. It is shown that, in many cases, the hybrid QM /MM potential behaves better than do related MNDO /M , AM 1, and PM 3 methods. As a case in point, the draw-back of AM 1 favoring bifurcated H-bonded structures over single ones is not presented in the combined AM 1/OPLS scheme. Possible ways of improvement of the combined QM /MM potential are discussed. © 1992 John Wiley & Sons, Inc.     

Proton transfer and associated molecular rearrangements in the photocycle of photoactive yellow protein: role of water molecular migration on the proton transfer reaction

The mechanism of the proton transfer and the concomitant molecular structural and hydrogen bond rearrangements after the photoisomerization of the chromophore in the photocycle of photoactive yellow protein are theoretically investigated by using the QM/MM method and molecular dynamics calculations. The free energy surface along this proton-transfer process is determined. This work suggests the important role of the water molecular migration into the moiety of chromophore, which facilitates proton transfer by the hydrogen bond rearrangement and the hydration of the pB' state.     

Photoinduced electron and proton transfer in the hydrogen-bonded pyridine-pyrrole system

We present here a detailed analysis of the mechanism of photoinduced electron and proton transfer in the planar pyrrole-pyridine hydrogen-bonded system, a model for the photochemistry of hydrogen bonds in DNA base pairs. Two different crossings, an avoided crossing and a conical intersection, are the key steps for forward and backward electron and proton transfer providing to the system photostability against UV radiation by restoring the system in its initial electronic and geometric structure.     

Microwave spectrum of methoxyacetic acid: assignment of the hydrogen-bonded rotamer

Microwave spectra of CH₃OCH₂COOH and CH₃OCH₂COOD are reported. One conformation has been assigned. This form of the molecule has a planar HCOCCOOH skeleton with four out-of-plane hydrogens. A weak five-membered intramolecular hydrogen bond is formed between the hydroxyl proton and the ether oxygen thus stabilizing the planar form. Absolute intensity measurements and arguments based on a few reasonable assumptions have been used to show that the assigned rotamer is present at concentrations amounting to between 10 and 30 per cent of the total. Other forms are not identified. Seven vibrationally excited states were assigned and attributed to the three lowest torsional modes. The dipole moment was determined to be μ_a = 4.72±0.04 D, μ_b = 0.15±0.02 D, and μ_total = 4.72±0.04 D.