Ab initio molecular dynamics study of proton transport in imidazolium-based ionic liquids with added imidazole.

Development of efficient anhydrous proton-conducting materials would expand the operational temperature ranges of hydrogen fuels cells (HFCs) and eliminate their dependence on maintaining sufficient hydration levels to function efficiently. Protic ionic liquids (PILs), which have high ionic densities and low vapor pressures, have emerged as a potential material for proton conducting layers in HFCs. In this work, we investigate proton transport via the Grotthuss mechanism in 1-ethylimidazolium bis-(trifluoromethanesulfonyl)imide ([C2HIm][TFSI]) protic ionic liquids with added imidazole (Im0) using ab initio molecular dynamics. In particular, we vary the composition of the systems studied from pure [C2HIm][TFSI] to those where the mole fraction of Im0 is 0.67. Given the large difference in pKa between C2HIm+ and HTFSI, TFSI- does not accept acidic protons from C2HIm+; conversely, imidazolium (HIm+) and C2HIm+ have very similar pKa values, and thus Im0 can readily accept protons. We find that the unprotonated nitrogen on Im0 dominates solvation of the labile protons on C2HIm+ and other Im0 species, resulting in formation of robust imidazole wires. Given the amphoteric nature of Im0, i.e. its ability to accept and donate protons, these wires provide conduits along which protons can rapidly traverse via the Grotthuss mechanism, thereby greatly increasing the proton coefficient of self-diffusion. We find that the average length of the wires increases with added Im0, and thus as the mole fraction of Im0 increases so too does the proton diffusion constant. Lastly, we analyze our trajectories to determine the energy and time scales associated with proton transfer.

The hopping mechanism of the hydrated excess proton and its contribution to proton diffusion in water.

In this work, a series of analyses are performed on ab initio molecular dynamics simulations of a hydrated excess proton in water to quantify the relative occurrence of concerted hopping events and "rattling" events and thus to further elucidate the hopping mechanism of proton transport in water. Contrary to results reported in certain earlier papers, the new analysis finds that concerted hopping events do occur in all simulations but that the majority of events are the product of proton rattling, where the excess proton will rattle between two or more waters. The results are consistent with the proposed "special-pair dance" model of the hydrated excess proton wherein the acceptor water molecule for the proton transfer will quickly change (resonate between three equivalent special pairs) until a decisive proton hop occurs. To remove the misleading effect of simple rattling, a filter was applied to the trajectory such that hopping events that were followed by back hops to the original water are not counted. A steep reduction in the number of multiple hopping events is found when the filter is applied, suggesting that many multiple hopping events that occur in the unfiltered trajectory are largely the product of rattling, contrary to prior suggestions. Comparing the continuous correlation function of the filtered and unfiltered trajectories, we find agreement with experimental values for the proton hopping time and Eigen-Zundel interconversion time, respectively.

Simulation study of the effects of phase separation on hydroxide solvation and transport in anion exchange membranes.

Anion exchange membranes (AEMs) can be cheaper alternatives than proton exchange membranes, but a key challenge for AEMs is to archive good ionic conductivity while maintaining mechanical strength. Diblock copolymers containing a mechanically strong hydrophobic block and an ion-conducting hydrophilic block have been shown to be viable solutions to this challenge. Using our recently developed reactive hydroxide model, we investigate the effects of block size on the hydroxide solvation and transport in a diblock copolymer (PPO-b-PVBTMA) in its highly hydrated state. Typically, both hydroxide and water diffusion constants decrease as the hydrophobic PPO block size increases. However, phase separation takes place above a certain mole ratio of hydrophobic PPO to hydrophilic PVBTMA blocks and we found it to effectively recover the diffusion constants. Extensive analyses reveal that morphological changes modulate the local environment for hydroxide and water transport and contribute to that recovery. The activation energy barriers for hydroxide and water diffusion show abrupt jumps at the same block ratios when such recovery effects begin to appear, suggesting transformation of the structure of water channels. Taking the advantages of partial phase separation can help optimize both ionic conductivity and mechanical strength of fuel cell membranes.

Development of reactive force fields using ab initio molecular dynamics simulation minimally biased to experimental data.

Incorporation of quantum mechanical electronic structure data is necessary to properly capture the physics of many chemical processes. Proton hopping in water, which involves rearrangement of chemical and hydrogen bonds, is one such example of an inherently quantum mechanical process. Standard ab initio molecular dynamics (AIMD) methods, however, do not yet accurately predict the structure of water and are therefore less than optimal for developing force fields. We have instead utilized a recently developed method which minimally biases AIMD simulations to match limited experimental data to develop novel multiscale reactive molecular dynamics (MS-RMD) force fields by using relative entropy minimization. In this paper, we present two new MS-RMD models using such a parameterization: one which employs water with harmonic internal vibrations and another which uses anharmonic water. We show that the newly developed MS-RMD models very closely reproduce the solvation structure of the hydrated excess proton in the target AIMD data. We also find that the use of anharmonic water increases proton hopping, thereby increasing the proton diffusion constant.

Reactive molecular dynamics models from ab initio molecular dynamics data using relative entropy minimization.

We present two new multiscale molecular dynamics (MS-RMD) models for the hydrated excess proton in water developed directly from ab initio molecular dynamics (AIMD) simulation data of the same system. The potential of mean force along the proton transfer reaction coordinate and radial distribution functions for the MS-RMD models are shown faithfully reproduce those of AIMD. The models are developed using an algorithm based on relative entropy minimization, thus demonstrating the ability of the method to rapidly generate accurate and highly efficient reactive MD force fields.

Breaking the theoretical scaling limit for predicting quasiparticle energies: the stochastic GW approach.

We develop a formalism to calculate the quasiparticle energy within the GW many-body perturbation correction to the density functional theory. The occupied and virtual orbitals of the Kohn-Sham Hamiltonian are replaced by stochastic orbitals used to evaluate the Green function G, the polarization potential W, and, thereby, the GW self-energy. The stochastic GW (sGW) formalism relies on novel theoretical concepts such as stochastic time-dependent Hartree propagation, stochastic matrix compression, and spatial or temporal stochastic decoupling techniques. Beyond the theoretical interest, the formalism enables linear scaling GW calculations breaking the theoretical scaling limit for GW as well as circumventing the need for energy cutoff approximations. We illustrate the method for silicon nanocrystals of varying sizes with N_{e}>3000 electrons.

Electron transfer beyond the static picture: a TDDFT∕TD-ZINDO study of a pentacene dimer.

We use time-dependent density functional theory and time-dependent ZINDO (a semi-empirical method) to study transfer of an extra electron between a pair of pentacene molecules. A measure of the electronic transfer integral is computed in a dynamic picture via the vertical excitation energy from a delocalized anionic ground state. With increasing dimer separation, this dynamical measurement of charge transfer is shown to be significantly larger than the commonly used static approximation (i.e., LUMO+1-LUMO of the neutral dimer, or HOMO-LUMO of the charged dimer), up to an order of magnitude higher at 6 Å. These results offer a word of caution for calculations involving large separations, as in organic photovoltaics, where care must be taken when using a static picture to model charge transfer.

Near-field: a finite-difference time-dependent method for simulation of electrodynamics on small scales.

We develop near-field (NF), a very efficient finite-difference time-dependent (FDTD) approach for simulating electromagnetic systems in the near-field regime. NF is essentially a time-dependent version of the quasistatic frequency-dependent Poisson algorithm. We assume that the electric field is longitudinal, and hence propagates only a set of time-dependent polarizations and currents. For near-field scales, the time step (dt) is much larger than in the usual Maxwell FDTD approach, as it is not related to the velocity of light; rather, it is determined by the rate of damping and plasma oscillations in the material, so dt = 2.5 a.u. was well converged in our simulations. The propagation in time is done via a leapfrog algorithm much like Yee's method, and only a single spatial convolution is needed per time step. In conjunction, we also develop a new and very accurate 8 and 9 Drude-oscillators fit to the permittivity of gold and silver, desired here because we use a large time step. We show that NF agrees with Mie-theory in the limit of small spheres and that it also accurately describes the evolution of the spectral shape as a function of the separation between two gold or silver spheres. The NF algorithm is especially efficient for systems with small scale dynamics and makes it very simple to introduce additional effects such as embedding.

Modeling molecular effects on plasmon transport: silver nanoparticles with tartrazine.

Modulation of plasmon transport between silver nanoparticles by a yellow fluorophore, tartrazine, is studied theoretically. The system is studied by combining a finite-difference time-domain Maxwell treatment of the electric field and the plasmons with a time-dependent parameterized method number 3 simulation of the tartrazine, resulting in an effective Maxwell∕Schrödinger (i.e., classical∕quantum) method. The modeled system has three linearly arranged small silver nanoparticles with a radius of 2 nm and a center-to-center separation of 4 nm; the molecule is centered between the second and third nanoparticles. We initiate an x-polarized current on the first nanoparticle and monitor the transmission through the system. The molecule rotates much of the x-polarized current into the y-direction and greatly reduces the overall transmission of x-polarized current.