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Benzoquinones can undergo reversible reductions and are attractive candidates for use as active materials in green carbon-based batteries. Related compounds of potential utility include 4,4'-diphenoquinones, which have extended quinonoid structures with two carbonyl groups in different rings. Diphenoquinones are a poorly explored class of compounds, but a wide variety can be synthesized, isolated, crystallized, and fully characterized. Experimental and computational approaches have established that typical 4,4'-diphenoquinones have nearly planar cores in which two cyclohexadienone rings are joined by an unusually long interannular C═C bond. Derivatives unsubstituted at the 3,3',5,5'-positions react readily by hydration, dimerization, and other processes. Association of diphenoquinones in the solid state normally produces chains or sheets held together by multiple C-H···O interactions, giving structures that differ markedly from those of the corresponding 4,4'-dihydroxybiphenyls. Electrochemical studies in solution and in the solid state show that diphenoquinones are reduced rapidly and reversibly at potentials higher than those of analogous benzoquinones. Together, these results help bring diphenoquinones into the mainstream of modern chemistry and provide a foundation for developing redox-active derivatives for use in carbon-based electrochemical devices.

Quinonoid compounds play central roles as redox-active agents in photosynthesis and respiration and are also promising replacements for inorganic materials currently used in batteries. To design new quinonoid compounds and predict their state of protonation and redox behavior under various conditions, their pKa values must be known. Methods that can predict the pKa values of simple phenols cannot reliably handle complex analogues in which multiple OH groups are present and may form intramolecular hydrogen bonds. We have therefore developed a straightforward method based on a linear relationship between experimental pKa values and calculated differences in energy between quinols and their deprotonated forms. Simple adjustments allow reliable predictions of pKa values when intramolecular hydrogen bonds are present. Our approach has been validated by showing that predicted and experimental values for over 100 quinols and related compounds differ by an average of only 0.3 units. This accuracy makes it possible to select proper pKa values when experimental data vary, predict the acidity of quinols and related compounds before they are made, and determine the sites and orders of deprotonation in complex structures with multiple OH groups.

Benzoquinone and hydroquinone cocrystallize to form quinhydrone, a 1:1 complex with a characteristic structure in which the components are positioned by hydrogen bonds and charge-transfer interactions. We have found that analogous diphenoquinhydrones can be made by combining 4,4'-diphenoquinones with the corresponding 4,4'-dihydroxybiphenyls. In addition, mixed diphenoquinhydrones can be assembled from components with different substituents, and mismatched quinhydrones can be made from benzoquinones and dihydroxybiphenyls. In all cases, the components of the resulting structures are linked in alternation by O-H···O hydrogen bonds to form essentially planar chains, which stack to produce layers in which π-donors and π-acceptors are aligned by charge-transfer interactions. Geometric parameters, computational studies, and spectroscopic properties of diphenoquinhydrones show that the key intermolecular interactions are stronger than those in simple quinhydrone analogues. These findings demonstrate that the principles of modular construction underlying the formation of classical quinhydrones can be generalized to produce a broad range of hydrogen-bonded charge-transfer materials in which the components are positioned by design.

Copper-catalyzed Csp-S cross-coupling is known to form rare macrocyclic alkynyl sulfides. Computational studies now suggest a mechanism for the reaction pathway. Upon formation of Cu-S species, subsequent α-addition/elimination at the ethynylic carbon affords the desired macrocycle.

Quinonoid compounds play central roles as redox-active agents in photosynthesis and respiration and are also promising replacements for inorganic materials currently used in batteries. To design new quinonoid compounds and predict their state of protonation and redox behavior under various conditions, their p

The proton transfer mechanisms involved inside aqueous, solvent-separated encounter complexes between phenol and carboxyl moieties are studied using ab initio molecular dynamics and computational time-resolved vibrational spectroscopy. This model framework can be viewed as a ground-state analog of the excited-state proton transfer reactions that have been actively investigated using ultrafast spectroscopy. Three qualitatively distinct proton transfer pathways are observed in the simulations. These can be described as direct concerted, direct sequential, and through bulk transfers. The primary difference between the sequential and concerted mechanism is the involvement of a reaction intermediate in which the proton fluctuates for several picoseconds through the hydrogen bonds connecting donor and acceptor but resides primarily on an intervening water molecule in the encounter complex. These results contribute to our molecular level understanding of the diverse processes involved in proton transfer within water-separated encounter complexes.

Acid ionization and dissociation are phenomena that play a fundamental role in chemistry and biology, but their microscopic details are largely unknown. We use ab initio molecular dynamics to identify and characterize various structures that are formed along the pathway of dissociation of trifluoroacetic acid (pK(a) = 0.5). The present results demonstrate that solutions of moderately strong (-1or= pK(a)or= 1) carboxylic acids contain significant quantities of at least two forms whose bonding patterns are intermediate between those of covalent and dissociated structures, R-COOH...OH(2) and R-COO(-)(aq) + H(3)O(+)(aq), respectively. The first is a proton-shared structure of the form R-COO(delta-).H.(delta+)OH(2) which can be distinguished from the covalent form by its characteristic "continuous" absorption below 1700 cm(-1). The second is a contact ion pair whose average structure can be written as R-COO(-).H(3)O(+). We demonstrate that the transformation of proton-shared into contact ion pair forms coincides with the disappearance of the carbonyl vibration mode centered around 1720 cm(-1) and the appearance of the asymmetric and symmetric carboxylate [Formula: see text] vibration modes at 1620 and 1380 cm(-1), respectively. The aforementioned transformation is accompanied by significant changes in the first solvation shell of the acid molecule which we discuss.

Cryogenic conditions favor the formation of ion-pair dissociation intermediates in amorphous mixtures of HF and H(2)O, making possible their characterization by means of infrared spectroscopy. The experimental infrared spectra show a structurally rich "continuous" absorption ranging from 1000 to 3400 cm(-1), which, in principle, contains important information regarding the microscopic structure of the aforementioned dissociation intermediates. Herein, we demonstrate that this microscopic information can be extracted by comparing and contrasting experimental spectra with those obtained by means of carefully designed first-principles molecular dynamics calculations. Very good, systematic agreement between theoretical and experimental spectra can be obtained for HF/H(2)O mixtures of various compositions, revealing the presence of proton-shared, dissociation intermediates F(delta-) * * * H * * * (delta+)OH(2). The existence of similar proton-shared, hydrogen-bonded intermediates of ionization, that are stable in solution, but not in the gas phase, has been previously suggested by other groups, using, among other techniques, low temperature NMR data and aprotic, dipolar, solvents. Our investigation reveals that similar structures are also stable in aqueous solutions of HF. We discuss some of the implications of the present findings as far as the mechanism of dissociation of weak acids is concerned.

We use ab initio molecular dynamics to study proton transfer in a donor-bridge-acceptor system in which the bridge is a single water molecule and the entire system is embedded in aqueous solution. The results, based on a large number of proton transfer trajectories, demonstrate that the dominant charge-transfer pathway is a subpicosecond "through bridge" event in which the bridge adopts an Eigen-like (hydronium) structure. We also identify another state in which the bridge forms a Zundel-like configuration with the acceptor that appears to be a dead end for the charge transfer. The reaction coordinate is inherently multidimensional and, as we demonstrate, cannot be given in terms of either local structural parameters of the donor-bridge-acceptor system or local solvent coordination numbers.

The methodology of ab initio molecular dynamics, wherein finite-temperature dynamical trajectories are generated by using forces computed “on the fly” from electronic structure calculations, has had a profound influence in modern theoretical research. Ab initio molecular dynamics allows chemical processes in condensed phases to be studied in an accurate and unbiased manner, leading to new paradigms in the elucidation of microscopic mechanisms, rationalization of experimental data, and testable predictions of new phenomena. The purpose of this work is to give a brief introduction to the technique and to review several important recent developments in the field. Several illustrative examples showing the power of the technique have been chosen. Perspectives on future directions in the field also will be given.

The ab initio molecular-dynamics formalism of Car and Parrinello is extended to preserve the locality of the orbitals. The supplementary term in the Lagrangian does not affect the nuclear dynamics, but ensures "on the fly" localization of the electronic orbitals within a periodic supercell in the Gamma-point approximation. The relationship between the resulting equations of motion and the formation of a gauge-invariant Lagrangian combined with a gauge-fixing procedure is briefly discussed. The equations of motion can be used to generate a very stable and easy to implement numerical integration algorithm. It is demonstrated that this algorithm can be used to compute the trajectory of the maximally localized orbitals, known as Wannier orbitals, in ab initio molecular dynamics with only a modest increase in the overall computer time. In the present paper, the new method is implemented within the generalized gradient approximation to Kohn-Sham density-functional theory employing plane wave basis sets and atomic pseudopotentials. In the course of the presentation, we briefly discuss how the present approach can be combined with localized basis sets to design fast linear scaling ab initio molecular-dynamics methods.

In this article, we propose an efficient method for sampling the relevant state space in condensed phase reactions. In the present method, the reaction is described by solving the electronic Schr\"{o}dinger equation for the solute atoms in the presence of explicit solvent molecules. The sampling algorithm uses a molecular mechanics guiding potential in combination with simulated tempering ideas and allows thorough exploration of the solvent state space in the context of an ab initio calculation even when the dielectric relaxation time of the solvent is long. The method is applied to the study of the double proton transfer reaction that takes place between a molecule of acetic acid and a molecule of methanol in tetrahydrofuran. It is demonstrated that calculations of rates of chemical transformations occurring in solvents of medium polarity can be performed with an increase in the cpu time of factors ranging from 4 to 15 with respect to gas-phase calculations., Comment: 15 pages, 9 figures. To appear in J. Chem. Phys

In this article the separability of the nuclear degrees of freedom system into mixed quantum and classical components is examined by looking at secondary kinetic isotope effects in a model proton transfer reaction. To explore this issue, the nature of secondary kinetic isotope effects is investigated by means of molecular mechanics and ab initio simulations of a model system in which intramolecular proton transfer occurs in a region whose chemical topology is similar to that of malonaldehyde. Isotope effects are calculated using importance sampling Monte Carlo techniques designed to improve the statistical efficiency of ab initio simulations within the framework of quantum centroid transition state theory. The ab initio results for kinetic isotope effects are contrasted with those obtained using two molecular mechanics potential energy functions. It is demonstrated that the calculated isotope effects are extremely sensitive to subtle features of the potential energy surface, which suggests that information from ab initio structure and energy calculations about configurations along the reaction path must be utilized in the construction of classical potentials to obtain accurate secondary kinetic isotope effect predictions. It is also demonstrated that quantum nuclear degrees of freedom of all secondary atoms that move significantly as a chemical reaction proceeds should be treated explicitly, as even secondary heavy-atom tunneling effects could be significant. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2003

The idea of using a dielectric continuum inside a molecule to accurately model molecular polarizability is extended to include a larger spectrum of bioorganic molecules and the condensed phase. Atomic polarization radii and an internal dielectric (ein) were fitted to reproduce ab initio B3LYP/aug-cc-pVTZ polarizability tensors taken from a data set of 707 molecules. The average unsigned error on the isotropic polarizability and anisotropy are 2.6% and 5.2%, respectively. It is shown that usual Poisson−Boltzmann contact radii and a low internal dielectric are not appropriate and require major revision. To account for the anisotropy of polarizability, the internal dielectric (ein) constant needs to be larger than 6.0. Reinterpreting the theoretical link between ein and the experimental refractive index (n), this study shows, with a set of 23 organic molecules spanning the entire range of n, that even with ein = 24 the obtained refractive indices can correlate well with experiment (slope of 1.00, intercept o...

In this article the tautomerization reaction of the enol form of malonaldehyde is used to investigate the magnitude and origin of changes in centroid transition state theory proton transfer reaction rate predictions caused by the quantum dispersion of heavy nuclei. Using an empirical valence bond method to construct the potential energy surface, it is found that quantization of the nuclear degrees of freedom of the carbon atoms significantly influences the centroid potential of mean force used to describe the proton transfer reaction. In contrast, an ab initio simulation carried out using a recently developed molecular mechanics based importance sampling method [J. Chem. Phys. 114, 6763 (2001)] in combination with an accurate density functional theory evaluation of the electronic energies shows a substantially smaller influence of the quantum nuclear degrees of freedom of the secondary atoms on the centroid potential of mean force. A detailed analysis of the different influence of quantization of the nucl...

The aluminum oxihydroxide boehmite (γ-AlOOH) is the topotactic precursor of γ-alumina, widely used as a support of refining catalysts. We use ab initio calculations and molecular dynamics (MD) to study water–boehmite interfacial properties, which are believed to play a key role during the industrial synthesis of boehmite in aqueous solution. For four relevant crystallographic planes—(010), (100), (001), and (101)—we develop a theoretical approach for calculating surface energies and interfacial energies that cannot be determined experimentally. From these values, the morphology of boehmite nanosized particles is constructed either in vacuum or in water, highlighting the strong effect of the solvent. It is clearly shown that during MD water molecules react on the surfaces by molecular adsorption and dissociative chemisorption, producing surface hydroxyl groups. A detailed analysis of the local structure before and after water adsorption is furnished. Particularly, four main surface hydroxyl groups are identified by their stretching vibrational frequencies: μ 2 -Al VI (ν OH =3676 cm −1 ), μ 1 -Al VI (ν OH =3712 cm −1 ), μ 1 -Al V (ν OH =3741 cm −1 ), and μ 1 -Al IV (ν OH =3819 cm −1 ). This analysis of surface hydroxyl groups gives us some new insights for the understanding of experimental IR band assignment and Bronsted acidity by ammonia adsorption. The localization of basic and acid Bronsted sites on the boehmite nanosized particles is resolved. An interpretation of these results in the light of γ-alumina is attempted.

In this article, the classical potential based importance Monte Carlo sampling method of Iftimie et al. [J. Chem. Phys. 113, 4852, (2000)] is applied to an ab initio simulation of the proton transfer tautomerization reaction of malonaldehyde in an aprotic, nonpolar solvent. It is demonstrated that ad hoc bond-energy bond-order relations derived from bond evolution theory combined with Pauling’s valence bond ideas can be used to construct a molecular mechanics guidance potential for the simulation of the proton transfer reaction which improves the statistics of the calculation by three orders of magnitude. The sampling method is extended to simulations in which quantum effects are treated using the imaginary time path-integral representation. A new algorithm based on multiple Markov chain theory is introduced by which it is possible to obtain very short integrated correlation lengths in calculations of quantum static correlation functions.

We show computational evidence that ground-state moderately strong hydroxyarenes (Ar-OH, pKa ∼ 0) dissociate by forming an ion-pair intermediate that lives for 3-5 ps. The concentration of this intermediate is approximately 2 times smaller than that of the un-ionized acid at pH ∼ 0.6 and is characterized by average C-O bond lengths (1.30 A) that are intermediate between those of un-ionized (1.29 A) and fully dissociated (1.34 A) species. During the lifetime of the ion-pair intermediate the excess proton fluctuates between the oxygen atom of the phenolic moiety and those of water molecules in the first and second solvation shells on a subpicosecond time scale (∼100-300 fs).

Ultrafast, time-resolved investigations of acid-base neutralization reactions have recently been performed using systems containing the photoacid 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (HPTS) and various Bronsted bases. Two conflicting neutralization mechanisms have been formulated by Mohammed et al. [Science 310, 83 (2005)] and Siwick et al. [J. Am. Chem. Soc. 129, 13412 (2007)] for the same acid-base system. Herein an ab initio molecular dynamics based computational model is formulated, which is able to investigate the validity of the proposed mechanisms in the general context of ground-state acid-base neutralization reactions. Our approach consists of using 2,4,6-tricyanophenol (exp. pKa congruent with 1) as a model for excited-state HPTS( *) (pKa congruent with 1.4) and carboxylate ions for the accepting base. We employ our recently proposed dipole-field/quantum mechanics (QM) treatment [P. Maurer and R. Iftimie, J. Chem. Phys. 132, 074112 (2010)] of the proton donor and acceptor molecules. This approach allows one to tune the free energy of neutralization to any desired value as well as model initial nonequilibrium hydration effects caused by a sudden increase in acidity, making it possible to achieve a more realistic comparison with experimental data than could be obtained via a full-QM treatment of the entire system. It is demonstrated that the dipole-field/QM model reproduces correctly key properties of the 2,4,6-tricyanophenol acid molecule including gas-phase proton dissociation energies and dipole moments, and condensed-phase hydration structure and pKa values.

Recently, the vacuum-phase molecular polarizability tensor of various molecules has been accurately modeled (Truchon et al., J Chem Theory Comput 2008, 4, 1480) with an intramolecular continuum dielectric model. This preliminary study showed that electronic polarization can be accurately modeled when combined with appropriate dielectric constants and atomic radii. In this article, using the parameters developed to reproduce ab initio quantum mechanical (QM) molecular polarizability tensors, we extend the application of the “electronic polarization from internal continuu” (EPIC) approach to intermolecular interactions. We first derive a dielectric-adapted least-square-fit procedure similar to RESP, called DRESP, to generate atomic partial charges based on a fit to a QM abinitio electrostatic potential (ESP). We also outline a procedure to adapt any existing charge model to EPIC. The ability of this to reproduce local polarization, as opposed to uniform polarization, is also examined leading to an induced ESP relative root mean square deviation of 1%, relative to ab initio, when averaged over 37 molecules including aromatics and alkanes. The advantage of using a continuum model as opposed to an atom-centered polarizable potential is illustrated with a symmetrically perturbed atom and benzene. We apply EPIC to a cation-π binding system formed by an atomic cation and benzene and show that the EPIC approach can accurately account for the induction energy. Finally, this article shows that the ab initio electrostatic component in the difficult case of the H-bonded 4-pyridone dimer, a highly polar and polarized interaction, is well reproduced without adjusting the vacuum-phase parameters. © 2009 Wiley Periodicals, Inc. J Comput Chem 2010

The bandgap and band bowing parameter of semiconductor alloys are calculated with a fast and realistic approach. The method is a dielectric scaling approximation that is based on a scissor approximation. It adds an energy shift to the bandgap provided by the local density approximation (LDA) of the density functional theory (DFT). The energy shift consists of a material-independent constant weighted by the inverse of the high-frequency dielectric constant. The salient feature of the approach is the fast calculation of the dielectric constant of alloys via the Green function (GF) of the TB-LMTO (tight-binding linear muffin-tin orbitals) in the atomic sphere approximation (ASA). When it is applied to highly mismatched semiconductor alloys (HMAs) like Zn Te$_x$ Se$_{1-x}$, this method provides a band bowing parameter that is different from the band bowing parameter calculated with the LDA due to the bowing exhibited also by the high-frequency dielectric constant., 6 pages, 2 figure, accepted in Solid State Communications

Dipole polarizabilities of individual ions and molecules are computed from first principles in three condensed-phase systems: pure water, pure hydrofluoric acid, and an equimolar mixture of water and hydrofluoric acid in which HF is mostly ionized. We find that the polarizability of fluorine and oxygen centers varies linearly with the value of the bond order, which measures the local degree of advancement of the ionization reaction F-H+H(2)O==[F(delta-).H.(delta+)OH(2)]==F(-)+H(3)O(+). This observation explains the validity of the Lorentz-Lorenz formula for mixtures of acids and water and could have important practical consequences concerning the construction of empirical polarizable reactive force fields. Our results are consistent with the Mulliken charge-transfer picture of proton transfer reactions. The present results also suggest that the average isotropic polarizability of a chemical entity changes substantially only when that entity is involved in charge-transfer processes.

The existence of a broad, mid-infrared absorption ranging from 1000 to 3000 cm(-1) is usually interpreted as a signature for the existence of protonated water networks. Herein, we use cryogenic mixtures of water and hydrogen fluoride (HF) and show experimental and computational evidence that similarly wide absorptions can be generated by a broad distribution of proton-shared and ion pair complexes. In the present case, we demonstrate that the broadening is mainly inhomogeneous, reflecting the fact that the topology of the first solvation shell determines the local degree of ionization and the shared-proton asymmetric stretching frequency within H2O x HF complexes. The extreme sensitivity of the proton transfer potential energy hypersurface to local hydrogen bonding topologies modulates its vibrational frequency from 2800 down to approximately 1300 cm(-1), the latter value being characteristic of solvation geometries that yield similar condensed-phase proton affinities for H2O and fluoride. By linking the local degree of ionization to the solvation pattern, we are able to propose a mechanism of ionization for HF in aqueous solutions and to explain some of their unusual properties at large concentrations. However, an important conclusion of broad scientific interest is our prediction that spectral signatures that are normally attributed to protonated water networks could also reveal the presence of strong hydrogen bonds between un-ionized acids and water molecules, with important consequences to spectroscopic investigations of biologically relevant proton channels and pumps.

The properties of N-methylacetamide along a cis-trans isomerization pathway described by twisting about the C(O)-N bond are examined at finite temperature both in vacuo and in explicit water solvent. Two distinctly different theoretical descriptions, an ab initio (DFT-BLYP) and an empirical (CHARMM22) model, are studied in order to permit an assessment of the dominant forces active in the system. An analysis of the solvent structure at equilibrium and changes in solvation structure accompanying isomerization is, therefore, given for each model. Many-body polarization effects absent under CHARMM22 but present in the ab initio model are found to have a profound influence on the system. The electronic structure of the NMA molecule predicted by the ab initio method along the reaction coordinate is examined in order to shed further light on changes in peptide "partial-double" bond character [C(O)-N] as isomerization takes place. A new statistical-mechanical interpretation of the entropy change during a chemical reaction is presented to help interpret the thermochemistry of the simple reaction.

Spin-dependent tunneling through an indirect-band-gap barrier like the $\mathrm{GaAs}∕\mathrm{AlAs}∕\mathrm{GaAs}$ heterostructure along the $[001]$ direction is studied by the tight-binding method. The tunneling is characterized by the proportionality of the Dresselhaus Hamiltonians at the $\ensuremath{\Gamma}$ and $X$ points in the barrier and by Fano resonances (i.e., pairs of resonances and antiresonances or zeros in transmission). The present results suggest that large spin polarization can be obtained for energy windows that significantly exceed the spin splitting. The widths of these energy windows are mainly determined by the energy difference between the resonance and its associated zero, which in turn increases with the decrease of barrier transmissibility at direct tunneling. We formulate two conditions that are necessary for the existence of energy windows with large polarization. First, the resonances must be well separated such that their corresponding zeros are not pushed away from the real axis by mutual interaction. Second, the relative energy order of the resonances in the two spin channels must be the same as the order of their corresponding zeros. The degree to which the first condition is satisfied is determined by the barrier width and the longitudinal effective mass at the $X$ point. In contrast, the second condition can be satisfied by choosing an appropriate combination of spin splitting strength at the $X$ point and transmissibility through the direct barrier.

dissociation process of the weak acid HA has been the object of numerous experimental and theoretical investigations, which have focused on the chemical nature of the solvated reactants and products and stable or transient intermediate structures. However, the deceptive simplicity of reaction (1) masks a wealth of microscopic behavior that remains largely unexplained. Important insights into the dissociation mechanism can be gleaned from infrared (IR) spectra of aqueous solutions of weak acids. In particular, the IR spectra of these acids exhibit a broad absorption band extending from the lower range of the OH stretch band of water at n= 3000 cm 1 to the HOH bending peak at n= 1500 cm 1 and in some instances all the way down to the onset of the water libration band at n= 1000 cm . This “continuum of absorption” is reminiscent of that seen for solutions of strong acids, where its origin can be explained in terms of frequent protontransfer events between H3O + and H2O units. In the case of weak acids, however, the early transmission spectroscopy investigations of Leuchs and Zundel as well as the more recent attenuated total reflection measurements of Max and Chapados strongly suggest that it is either the unionized hydrated acid HA(aq) or some relatively stable supramolecular

The theoretical principles underpinning the calculation of infrared spectra for condensed-phase systems in the context of ab initio molecular dynamics have been recently developed in literature. At present, most ab initio molecular dynamics calculations are restricted to relatively small systems and short simulation times. In this paper we devise a method that allows well-converged results for infrared spectra from ab initio molecular dynamics simulations using small systems and short trajectories characteristic of simulations typically performed in practice. We demonstrate the utility of our approach by computing the imaginary part of the dielectric constant epsilon"(omega) for H2O and D2O in solid and liquid phases and show that it compares well with experimental data. We further demonstrate that maximally localized Wannier orbitals can be used to separate the individual contributions of different molecular species to the linear spectrum of complex systems. The new spectral decomposition method is shown to be useful in present-day ab initio molecular dynamics calculations to compute the magnitude of the "continuous absorption" generated by excess protons in aqueous solutions with good accuracy even when other species present in the solutions absorb strongly in the same frequency window.

The cis−trans isomerization of N-methylacetamide, a molecular model of the polypeptide chain, is examined via umbrella sampling Car−Parrinello MD and classical MD, in both gas and solution phases at 300 K. A new analysis of the C(O)−N bond interconversion and a full examination of the solvent shell structure are presented.

Techniques from gauge-field theory are employed to derive an alternative formulation of the Car-Parrinello ab initio molecular-dynamics method that allows maximally localized Wannier orbitals to be generated dynamically as the calculation proceeds. In particular, the Car-Parrinello Lagrangian is mapped onto an SU(n) non-Abelian gauge-field theory and the fictitious kinetic energy in the Car-Parrinello Lagrangian is modified to yield a fully gauge-invariant form. The Dirac gauge-fixing method is then employed to derive a set of equations of motion that automatically maintain orbital locality by restricting the orbitals to remain in the "Wannier gauge." An approximate algorithm for integrating the equations of motion that is stable and maintains orbital locality is then developed based on the exact equations of motion. It is shown in a realistic application (64 water molecules plus one hydrogen-chloride molecule in a periodic box) that orbital locality can be maintained with only a modest increase in CPU time. The ability to keep orbitals localized in an ab initio molecular-dynamics calculation is a crucial ingredient in the development of emerging linear scaling approaches.

We investigate the role played by the coordination state of pre-existing water wires during the dissociation of moderately strong acids by means of first-principles molecular dynamics calculations. By preparing 2,4,6-tricyanophenol (calc. pKa∼0.5) in two different initial states, we are able to observe sequential as well as concerted trajectories of dissociation: On one hand, equilibrium dissociation takes place on a ∼50 ps timescale; proton conduction occurs through three-coordinated water wires in this case, by means of sequential Grotthus hopping. On the other hand, by preparing 2,4,6-tricyanophenol in a hydration state inherited from that of equilibrated phenol (calc. pKa = 7.6), the moderately strong acid finds itself in a presolvated state from which dissociation can take place on a ∼1 ps timescale. In this case, concerted dissociation trajectories are observed, which consist of proton translocation through two intervening, four-coordinated, water molecules in 0.1–1.0 ps. The present results suggest that, in general, the mechanism of proton translocation depends on how the excess proton is injected into a hydrogen bond network. In particular, if the initial conditions favour proton release to a fourfold H-bonded water molecule, proton translocation by as much as 6–8 A can take place on a sub-picosecond timescale.

We introduce a novel approach to compute dissociation free energy and entropy values in simulations that employ a density functional theory description of the acidic moiety and of the solvent. The approach consists of utilizing an alchemical transformation of a weak acid A-COOH into the strong acid B-COOH, which makes it practical to employ alchemical free energy perturbation methods in the context of ab initio molecular dynamics simulations. The present alchemical transformation circumvents the need to tackle changes in the total number of electrons and atoms by replacing the chemical residue responsible for the change in acidity with an easily tunable external effective potential. Our investigation demonstrates that (1) a simple but effective class of external potentials that control acidity changes in the acetic/trifluoroacetic acid series can be achieved by replacing the methyl and trifluoromethyl substituents by screened dipoles. Using this dipole-field/quantum-mechanics (DF/QM) approach one can predict gas-phase geometries, proton dissociation energies, total dipole moments, and water binding energies in good agreement with full-QM values. (2) The resulting alchemical perturbation calculations are stable and well converged and allow one to compute absolute pK(a) values whose accuracy is limited primarily by the exchange-correlation functional employed: H-COOH=2.5+/-0.6 (full-QM calculation), 3.7 (exp); F(3)C-COOH=0.4+/-0.6 (DF/QM calculation), 0.5 (exp); H(3)C-COOH=3.1+/-0.7 (DF/QM calculation), 4.7 (exp); 3) Our DF/QM model predicts that the difference in acidity between H-COOH and H(3)C-COOH is dominated by solvent entropy effects, in excellent agreement with experimental observations. The calculated difference between the dissociation energies of these acids is DeltaDelta(d)U=0.0+/-0.26 kcal/mol while the experimental value is 0.0+/-0.1 kcal/mol.

In this paper the ab initio potential of mean force for the formic acid–water system is calculated in a Monte Carlo simulation using a classical fluctuating charge molecular mechanics potential to guide Monte Carlo updates. The ab initio energies in the simulation are calculated using density-functional theory (DFT) methods recently developed by Salahub et al. [J. Chem. Phys. 107, 6770 (1997)] to describe hydrogen-bonded systems. Importance sampling methods are used to investigate structural changes and it is demonstrated that using a molecular mechanics importance function can improve the efficiency of a DFT simulation by several orders of magnitude. Monte Carlo simulation of the system in a canonical ensemble at T=300 K reveals two chemical processes at intermediate time scales: The rotation of the H2O bonded to HCOOH, which takes place on a time scale of 3 ps, and the dissociation of the complex which occurs in 24 ps. It is shown that these are the only important structural “reactions” in the formic ac...