Understanding the effects of electronic polarization and delocalization on charge-transport levels in oligoacene systems.

Electronic polarization and charge delocalization are important aspects that affect the charge-transport levels in organic materials. Here, using a quantum mechanical/embedded-charge (QM/EC) approach based on a combination of the long-range corrected ωB97X-D exchange-correlation functional (QM) and charge model 5 (CM5) point-charge model (EC), we evaluate the vertical detachment energies and polarization energies of various sizes of crystalline and amorphous anionic oligoacene clusters. Our results indicate that QM/EC calculations yield vertical detachment energies and polarization energies that compare well with the experimental values obtained from ultraviolet photoemission spectroscopy measurements. In order to understand the effect of charge delocalization on the transport levels, we considered crystalline naphthalene systems with QM regions including one or five-molecules. The results for these systems show that the delocalization and polarization effects are additive; therefore, allowing for electron delocalization by increasing the size of the QM region leads to the additional stabilization of the transport levels.

Charge-Transfer States in Organic Solar Cells: Understanding the Impact of Polarization, Delocalization, and Disorder.

We investigate the impact of electronic polarization, charge delocalization, and energetic disorder on the charge-transfer (CT) states formed at a planar C60/pentacene interface. The ability to examine large complexes containing up to seven pentacene molecules and three C60 molecules allows us to take explicitly into account the electronic polarization effects. These complexes are extracted from a bilayer architecture modeled by molecular dynamics simulations and evaluated by means of electronic-structure calculations based on long-range-separated functionals (ωB97XD and BNL) with optimized range-separation parameters. The energies of the lowest charge-transfer states derived for the large complexes are in very good agreement with the experimentally reported values. The average singlet-triplet energy splittings of the lowest CT states are calculated not to exceed 10 meV. The rates of geminate recombination as well as of dissociation of the triplet excitons are also evaluated. In line with experiment, our results indicate that the pentacene triplet excitons generated through singlet fission can dissociate into separated charges on a picosecond time scale, despite the fact that their energy in C60/pentacene heterojunctions is slightly lower than the energies of the lowest CT triplet states.

Molecular-Scale Understanding of Cohesion and Fracture in P3HT:Fullerene Blends.

Quantifying cohesion and understanding fracture phenomena in thin-film electronic devices are necessary for improved materials design and processing criteria. For organic photovoltaics (OPVs), the cohesion of the photoactive layer portends its mechanical flexibility, reliability, and lifetime. Here, the molecular mechanism for the initiation of cohesive failure in bulk heterojunction (BHJ) OPV active layers derived from the semiconducting polymer poly(3-hexylthiophene) [P3HT] and two monosubstituted fullerenes is examined experimentally and through molecular-dynamics simulations. The results detail how, under identical conditions, cohesion significantly changes due to minor variations in the fullerene adduct functionality, an important materials consideration that needs to be taken into account across fields where soluble fullerene derivatives are used.

Interfacial water properties in the presence of surfactants.

Water, because of its fundamental role in biology, geology, and many industrial applications and its anomalous behavior compared to that of simple fluids, continues to fascinate and attract extensive scientific interest. Building on previous studies of water in contact with different surfaces, in this study, we report results obtained from molecular dynamics simulations of water near hydrophilic and hydrophobic interfaces in the presence of nonionic and ionic amphiphilic molecules, hexaethylene glycol monododecyl ether (C12E6) and sodium dodecyl sulfate (SDS). We elucidate how these surfactants affect the packing (i.e., density profiles) and orientation of interfacial water. The results highlight the interplay of both surfactant charges and the substrate charge distribution predominantly with respect to the orientation of water molecules, up to distances longer than those expected based on simulation results on flat solid surfaces. We also quantify the dynamics of interfacial water molecules by computing the residence probability for water in contact with various substrates. We compare our results to those previously obtained for interfacial water on silica and graphite and also with experimental sum-frequency vibrational spectroscopy results at the air-water interface in the presence of surfactants. Our analysis could be useful for a better understanding of interfacial water not only near solid substrates but also near self-assembled/aggregated molecules at a variety of interfaces.

Static and Dynamic Energetic Disorders in the C60, PC61BM, C70, and PC71BM Fullerenes.

We use a combination of molecular dynamics simulations and density functional theory calculations to investigate the energetic disorder in fullerene systems. We show that the energetic disorder evaluated from an ensemble average contains contributions of both static origin (time-independent, due to loose packing) and dynamic origin (time-dependent, due to electron-vibration interactions). In order to differentiate between these two contributions, we compare the results obtained from an ensemble average approach with those derived from a time average approach. It is found that in both amorphous C60 and C70 bulk systems, the degrees of static and dynamic disorder are comparable, while in the amorphous PC61BM and PC71BM systems, static disorder is about twice as large as dynamic disorder.

Bulk stress distributions in the pore space of sphere-packed beds under Darcy flow conditions.

In this paper, bulk stress distributions in the pore space of columns packed with spheres are numerically computed with lattice Boltzmann simulations. Three different ideally packed and one randomly packed configuration of the columns are considered under Darcy flow conditions. The stress distributions change when the packing type changes. In the Darcy regime, the normalized stress distribution for a particular packing type is independent of the pressure difference that drives the flow and presents a common pattern. The three parameter (3P) log-normal distribution is found to describe the stress distributions in the randomly packed beds within statistical accuracy. In addition, the 3P log-normal distribution is still valid when highly porous scaffold geometries rather than sphere beds are examined. It is also shown that the 3P log-normal distribution can describe the bulk stress distribution in consolidated reservoir rocks like Berea sandstone.

Influence of Molecular Shape on Solid-State Packing in Disordered PC61BM and PC71BM Fullerenes.

Molecular and polymer packings in pure and mixed domains and at interfacial regions play an important role in the photoconversion processes occurring within bulk heterojunction organic solar cells (OSCs). Here, molecular dynamics simulations are used to investigate molecular packing in disordered (amorphous) phenyl-C70-butyric acid-methyl ester (PC71BM) and its C60 analogue (PC61BM), the two most widely used molecular-based electron-accepting materials in OSCs. The more ellipsoidal character of PC71BM leads to different molecular packings and phase transitions when compared to the more spherical PC61BM. Though electronic structure calculations indicate that the average intermolecular electronic couplings are comparable for the two systems, the electronic couplings as a function of orientation reveal important variations. Overall, this work highlights a series of intrinsic differences between PC71BM and PC61BM that should be considered for a detailed interpretation and modeling of the photoconversion process in OSCs where these materials are used.

Molecular dynamics simulations of surfactants at the silica-water interface: anionic vs nonionic headgroups.

Understanding surfactant adsorption on surfaces at the molecular level will provide us with the ability to design specific surfactants for surface modification. We conducted molecular dynamics simulations for sodium dodecyl sulfate (SDS) and hexaethylene glycol monododecyl ether (C(12)E(6)) adsorbed on silica substrates with varying degree of hydroxylation. Our results shed light on the effects of hydroxylation on the surfactant aggregate morphology. The discrete charge distribution on the substrate surface appears to dictate both surfactant adsorption and aggregate morphology. The differences in aggregate morphology observed for anionic SDS and non-ionic C(12)E(6) on silica substrates are discussed quantitatively and compared to available experimental data.

Stabilization of aqueous carbon nanotube dispersions using surfactants: insights from molecular dynamics simulations.

Techniques for separating bundles of carbon nanotubes into homogeneous dispersion are still under development, although a few methods have been successful at the laboratory scale. Understanding the effective interactions between carbon nanotubes in the presence of dispersing agents will provide the necessary information to develop better methods and also to refine the existing ones. We present here results from all-atom molecular dynamics simulations for aqueous flavin mononucleotide (FMN), which has been found experimentally to efficiently separate single-walled carbon nanotubes (SWNTs) based on diameter and chirality. We report results for the aggregate morphology of FMN on SWNTs of different diameters, as well as the potential of mean force between (6,6) SWNTs in the presence of aqueous FMN. The results are compared to the potential of mean force between SWNTs in aqueous sodium dodecyl sulfate (SDS). Our detailed analysis is used to explain the role of FMN, water, and sodium ions in providing a strong repulsive barrier between approaching SWNTs.

Lateral confinement effects on the structural properties of surfactant aggregates: SDS on graphene.

The structure of aqueous sodium dodecyl sulfate (SDS) surfactant aggregates formed on small graphene sheets and graphene nanoribbons has been studied using all-atom molecular dynamics simulations. Because the edges of the carbonaceous supports confine laterally the surfactant aggregates, by changing the size of the support (diameter of graphene sheets and width of graphene nanoribbons) it is possible to investigate lateral confinement effects on the aggregate morphology. The results are compared to those available on graphite, with no lateral confinement. Aqueous SDS aggregates were studied on 2.0 nm, 5.0 nm, and 10.0 nm circular graphene sheets and on 2.0 and 5.0 nm wide graphene nanoribbons. For the first time our results show that, because of lateral confinement provided by the graphene edges, SDS yields multiple layers, hemispheres, hemicylinders or multiple hemispheres depending on the graphene size and shape. Results are quantified in terms of morphology of the surfactant aggregates, order parameter of the adsorbed surfactant aggregates, and number of water molecules at contact with the carbonaceous support.

C12E6 and SDS surfactants simulated at the vacuum-water interface.

The effect of surface coverage on the aggregate structure for the nonionic hexaethylene glycol monododecyl ether (C(12)E(6)) and anionic sodium dodecyl sulfate (SDS) surfactants at vacuum-water interface has been studied using molecular dynamics simulations. We report the aggregate morphologies and various structural details of both surfactants as a function of surface coverage. Our results indicate that C(12)E(6) tail groups orient less perpendicularly to the vacuum-water interface compared to SDS ones. Interfacial C(12)E(6) shows a transition from gaslike to liquidlike phases as the surface density increases. However, even at the largest coverage considered, interfacial C(12)E(6) aggregates show more disordered structures compared to SDS ones. Both surfactants exhibit a non-monotonic change in planar mobility as the available surface area per molecule varies. The results are interpreted on the basis of the molecular features of both surfactants, with particular emphasis on the properties of the surfactant heads, which are nonionic, long, and flexible for C(12)E(6), as opposed to ionic, compact, and rigid for SDS.

Curvature effects on the adsorption of aqueous sodium-dodecyl-sulfate surfactants on carbonaceous substrates: structural features and counterion dynamics.

The effect of substrate curvature on surfactant self-assembly has been studied using all-atom molecular-dynamics simulations. We studied aqueous sodium-dodecyl-sulfate (SDS) surfactants on graphite, on the outer surface of single walled carbon nanotubes (SWNTs) and within SWNTs. Our results reveal that although the chemical nature of the substrates is constant, the self-assembled structures change significantly as the curvature varies. For example, at large surface density, SDS surfactants yield micellar structures on graphite, layered self-assemblies outside SWNTs, and cylindrical lamellar structures inside SWNTs. Changes in substrate curvature as well as surfactant surface density affect significantly surfactant orientation and, more importantly, headgroup-headgroup distribution, headgroup-counterion packing, and counterion residence time next to the headgroups.

SDS surfactants on carbon nanotubes: aggregate morphology.

Although carbon nanotubes have attracted enormous research interest, their practical application is still hindered, primarily, by the difficulty of separating them into samples monodispersed in diameter, chirality, and length. Recent advances show that ultracentrifugating carbon nanotube dispersions stabilized by surfactants is a promising route for achieving the desired separation. For further perfectioning this procedure it is necessary to know how surfactants adsorb on nanotubes of different diameters, which determines the nanotube-surfactant aggregate effective density and the nanotube-nanotube potential of mean force. Because only limited experimental data are available to elucidate these phenomena, we report here an extensive all-atom molecular dynamics study on the morphology of sodium dodecyl sulfate (SDS) surfactant aggregates adsorbed on (6,6), (12,12), and (20,20) single walled carbon nanotubes at room conditions. Our calculations reveal that the nanotube diameter is the primary factor that determines the morphology of the aggregates because of a competition between the entropic and energetic advantage encountered by the surfactants when they wrap one nanotube, and the enthalpic penalty faced during this process due to bending of the surfactant molecule. The data are in qualitative agreement with the neutron scattering results reported by Yurekli et al. [J. Am. Chem. Soc. 2004, 126, 9902], and for the first time provide an atomic-level description helpful in designing better separation, as well as stabilization techniques for aqueous carbon nanotube dispersions.

Hydrogen-bond dynamics for water confined in carbon tetrachloride-acetone mixtures.

In a variety of biological scenarios water is found trapped within hydrophobic environments (e.g., ion channels). Its behavior under such conditions is not well understood and therefore is attracting enormous scientific attention. It is of particular interest to understand how the confining environment affects both the structure and dynamics of water. Within this scenario, we report molecular dynamics simulation results for water trapped in a mixture of acetone and carbon tetrachloride whose composition mimics the one employed in recently reported experiments [Gilijamse, J. J.; et al. Proc. Natl. Acad. Sci. U.S.A. 2005, 102, 3202]. We show here that the water molecules dissolved in the carbon tetrachloride-acetone mixture assemble in clusters of varying sizes, that the longevity of hydrogen bonds between confined water molecules strongly depends on the cluster size, and that hydrogen bonds last longer for small water clusters in confined water than they do in bulk water. The simulated FT-IR spectra for the confined water are shifted at longer frequencies compared to those observed for bulk liquid water. We discuss the dependence of the FT-IR spectrum on the size of the water clusters dispersed in the carbon tetrachloride-acetone matrix. We also study in detail the rotational orientation of the dispersed water molecules, and we discuss how the composition of the organic matrix affects the results. By enhancing the interpretation of the experimental data, our results contribute to developing a molecular-based understanding of the relationship between environment and water properties.

Role of counterion condensation in the self-assembly of SDS surfactants at the water-graphite interface.

The aggregate structure of sodium dodecyl sulfate (SDS) adsorbed at the graphite-water interface has been studied with the aid of molecular dynamics (MD) simulations. As expected, our results show that adsorbed SDS yields hemi-cylindrical micelles. The hemi-cylindrical aggregates in our simulations closely resemble all structural and morphological details provided by previous solution atomic force microscopy (AFM) experiments. More interestingly, our data indicate that SDS head groups do not provide a complete shield to the hydrophobic tails. Instead, we found regions in which the hydrophobic tails are exposed to the aqueous solution. By conducting a parametric study for SDS-like nonionic surfactants we show that electrostatic interactions between SDS head groups and counterions are responsible for the unexpected result. Our interpretation is corroborated by density profiles, analysis of the coordination states, and mean square displacement data for both the adsorbed SDS surfactants and the counterions in solution. Counterion condensation appears to be a physical phenomenon that could be exploited to direct the assembly of advanced nanostructured materials.