Advances in Computational Methods for Modeling Photocatalytic Reactions: A Review of Recent Developments.

Photocatalysis is a fascinating process in which a photocatalyst plays a pivotal role in driving a chemical reaction when exposed to light. Its capacity to harness light energy triggers a cascade of reactions that lead to the formation of intermediate compounds, culminating in the desired final product(s). The essence of this process is the interaction between the photocatalyst's excited state and its specific interactions with reactants, resulting in the creation of intermediates. The process's appeal is further enhanced by its cyclic nature-the photocatalyst is rejuvenated after each cycle, ensuring ongoing and sustainable catalytic action. Nevertheless, comprehending the photocatalytic process through the modeling of photoactive materials and molecular devices demands advanced computational techniques founded on effective quantum chemistry methods, multiscale modeling, and machine learning. This review analyzes contemporary theoretical methods, spanning a range of lengths and accuracy scales, and assesses the strengths and limitations of these methods. It also explores the future challenges in modeling complex nano-photocatalysts, underscoring the necessity of integrating various methods hierarchically to optimize resource distribution across different scales. Additionally, the discussion includes the role of excited state chemistry, a crucial element in understanding photocatalysis.

Quantum Machine Learning in Materials Prediction: A Case Study on ABO3 Perovskite Structures.

Quantum machine learning (QML), ML on quantum computers, offers a promising approach for discovering and screening novel materials. This study introduces a hybrid classical-quantum ML method using a variational quantum classifier to identify simple perovskite structures within a data set of ABO3 compounds. The model is trained using a data set of 397 known ABO3 compounds, with 254 perovskites and 143 non-perovskite structures labeled as +1 and -1, respectively. By considering feature correlation and eliminating less important features, the QML system achieves an optimal accuracy of 88% for training data and 87% for unseen test data. These results demonstrate the potential of QML in materials science classification tasks, even with limited training data, leveraging the intrinsic properties of quantum computation to enhance the investigation of materials. In addition, perspectives on QML applications in materials science are discussed.

Enhanced luminescence sensing performance and increased intrachain order in blended films of P3HT and cellulose nanocrystals.

Blended films comprising poly(butyl acrylate) (PBA)-grafted cellulose nanocrystals (CNCs) and poly(3-hexylthiophene) (P3HT), exhibited more intense photoluminescence (PL) and longer PL emission lifetimes compared to pristine P3HT films. Optical absorption and photoluminescence spectra indicated reduced torsional disorder i.e. enhanced backbone planarity in the P3HT@CNC blended composites compared to the bare P3HT. Such molecule-level geometrical modification resulted in both smaller interchain and higher intrachain exciton bandwidth in the blended composites compared to the bare P3HT, because of reduced interchain interactions and enhanced intrachain order. These results indicate a potential switch of the aggregation behavior from dominant H-aggregates to J-aggregates, supported by Raman spectroscopy. The reorganization of micromolecular structure and concomitant macroscopic aggregation of the conjugated polymer chains resulted in a longer conjugation length for the P3HT@CNC blended composites compared to the bare P3HT. Additionally, this nanoscale morphological change produced a reduction in the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gap of the blends, evidenced from optical absorption spectra. Classical molecular dynamics simulation studies predicted the probability of enhanced planarity in the polymer backbone following interactions with CNC surfaces. Theoretical results from density functional theory calculations corroborate the experimentally observed reduction of optical bandgap in the blends compared to bare P3HT. The blended composite outperformed the bare P3HT in nitro-group PL sensing tests with a pronounced difference in the reaction kinetics. While the PL quenching dynamics for bare P3HT followed Stern-Volmer kinetics, the P3HT@CNC blended composite exhibited a drastic deviation from the same. This work shows the potential of a functionalized rod-like biopolymer in tuning the optoelectronic properties of a technologically important polymeric organic semiconductor through control of the nanoscale morphology.

Computational Analysis of the SARS-CoV-2 RBD-ACE2-Binding Process Based on MD and the 3D-RISM Theory.

The binding process of angiotensin-converting enzyme 2 (ACE2) to the receptor-binding domain (RBD) of the severe acute respiratory syndrome-like coronavirus 2 spike protein was investigated using molecular dynamics simulation and the three-dimensional reference interaction-site model theory. The results suggested that the protein-binding process consists of a protein-protein approaching step, followed by a local structural rearrangement step. In the approaching step, the interprotein interaction energy decreased as the proteins approached each other, whereas the solvation free energy increased. As the proteins approached, the glycan of ACE2 first established a hydrogen bond with the RBD. Thereafter, the number of interprotein hydrogen bonds increased rapidly. The solvation free energy increased because of the desolvation of the protein as it approached its partner. The spatial distribution function of the solvent revealed the presence of hydrogen bonds bridged by water molecules on the RBD-ACE2 interface. Finally, principal component analysis revealed that ACE2 showed a pronounced conformational change, whereas there was no significant change in RBD.

A reply to: "Response to Comment on "Density Functional Theory and 3D-RISM-KH molecular theory of solvation studies of CO2 reduction on Cu-, Cu2O-, Fe-, and Fe3O4-based nanocatalysts"".

In response (Kovalenko and Neburchilov, J. Mol. MODEL: 28:33, 1) to the comment (Gusarov, J. Mol. MODEL: 27:344-354, 2), the authors avoided answering the main question about the incorrect intermediate state of CO2 + H2 reduction reaction studied by Kovalenko and Neburchilov (J. Mol. MODEL: 26:267-276, 3). The intermediate products of this reaction are well known and presented in the literature including the studies of Li and Kanan (J. Am. Chem. Soc. 134:7231-7234, 4); Feaster et al. (ACS Catal. 7:4822-4827, 5); Choi et al. (Sci. Rep. 7:41,207-41,210, 6); Kuhl et al. (Am. Chem. Soc. 136:14,107-14,113, 7); Kuhl et al. (Energy Environ. Sci. 5:7050-7059, 8); and Hatsukade et al. (Phys. Chem. Chem. Phys. 16:13,814-13,819, 9) referenced by Kovalenko and Neburchilov (J. Mol. MODEL: 26:267-276, 3). In particular, in Figs. 2(d), 3(d), 4(d), and 5(d) (Kovalenko and Neburchilov, J. Mol. MODEL: 26:267-276, 3), the orientation of carbon monoxide is opposite to Fig. 4 (Feaster et al., ACS Catal. 7:4822-4827, 5), Fig. 6(a) (Choi et al., Sci. Rep. 7:41,207-41,210, 6), Fig. 7 (Kuhl et al., Energy Environ. Sci. 5:7050-7059, 8), Fig. 7 (Hatsukade et al., Phys. Chem. Chem. Phys. 16:13,814-13,819, 9), and Fig. 2 (Gusarov, J. Mol. MODEL: 27:344-354, 2). This obvious fact which also comes from chemical properties of components should not be ignored.

Comment on "Density functional theory and 3D-RISM-KH molecular theory of solvation studies of CO2 reduction on Cu-, Cu2O-, Fe-, and Fe3O4-based nanocatalysts".

Recently, A. Kovalenko et al. reported the computational study of molecular structure and energetics of CO2 + H2 reduction reaction on Cu-, Cu2O-, Fe-, and Fe3O4-based nanocatalysts in the J. Mol. Model., 26, 267 (2020). The authors claim that they developed and tested the multiscale modeling description of this process by combining the periodical boundary condition density functional theory (PBC DFT) and molecular theory of solvation. However, due to inappropriate selection of intermediate strictures, in particular, the unfavorite structure of CO* adsorbed on Cu-, Cu2O-, Fe-, and Fe3O4-nanoparticles, and some inconsistency in preparation of initial structures by DFT approach, there are serious concerns about the correctness and quality of the presented results. In addition, by this comment, I would like to help other researchers working on the development of new catalysts for electrochemical reduction of CO2 to avoid further misunderstandings following this study.

Zinc phthalocyanine conjugated cellulose nanocrystals for memory device applications.

We present the electrical properties of zinc phthalocyanine covalently conjugated to cellulose nanocrystals (CNC@ZnPc). Thin films of CNC@ZnPc sandwiched between two gold electrodes showed pronounced hysteresis in their current-voltage characteristics. The layered metal-organic-metal sandwich devices exhibit distinct high and low conductive states when bias is applied, which can be used to store information. Density functional theory results confirmed wave function overlap between CNC and ZnPc in CNC@ZnPc, and helped visualize the lowest (lowest unoccupied molecular orbital) and highest molecular orbitals (highest occupied molecular orbital) in CNC@ZnPc. These results pave the way forward for all-organic electronic devices based on low cost, earth abundant CNCs and metallophthalocyanines.

Photocatalytic Mechanism Control and Study of Carrier Dynamics in CdS@C3N5 Core-Shell Nanowires.

We present a potential solution to the problem of extraction of photogenerated holes from CdS nanocrystals and nanowires. The nanosheet form of C3N5 is a low-band-gap (Eg = 2.03 eV), azo-linked graphenic carbon nitride framework formed by the polymerization of melem hydrazine (MHP). C3N5 nanosheets were either wrapped around CdS nanorods (NRs) following the synthesis of pristine chalcogenide or intercalated among them by an in situ synthesis protocol to form two kinds of heterostructures, CdS-MHP and CdS-MHPINS, respectively. CdS-MHP improved the photocatalytic degradation rate of 4-nitrophenol by nearly an order of magnitude in comparison to bare CdS NRs. CdS-MHP also enhanced the sunlight-driven photocatalytic activity of bare CdS NWs for the decolorization of rhodamine B (RhB) by a remarkable 300% through the improved extraction and utilization of photogenerated holes due to surface passivation. More interestingly, CdS-MHP provided reaction pathway control over RhB degradation. In the absence of scavengers, CdS-MHP degraded RhB through the N-deethylation pathway. When either hole scavenger or electron scavenger was added to the RhB solution, the photocatalytic activity of CdS-MHP remained mostly unchanged, while the degradation mechanism shifted to the chromophore cleavage (cycloreversion) pathway. We investigated the optoelectronic properties of CdS-C3N5 heterojunctions using density functional theory (DFT) simulations, finite difference time domain (FDTD) simulations, time-resolved terahertz spectroscopy (TRTS), and photoconductivity measurements. TRTS indicated high carrier mobilities >450 cm2 V-1 s-1 and carrier relaxation times >60 ps for CdS-MHP, while CdS-MHPINS exhibited much lower mobilities <150 cm2 V-1 s-1 and short carrier relaxation times <20 ps. Hysteresis in the photoconductive J-V characteristics of CdS NWs disappeared in CdS-MHP, confirming surface passivation. Dispersion-corrected DFT simulations indicated a delocalized HOMO and a LUMO localized on C3N5 in CdS-MHP. C3N5, with its extended π-conjugation and low band gap, can function as a shuttle to extract carriers and excitons in nanostructured heterojunctions, and enhance performance in optoelectronic devices. Our results demonstrate how carrier dynamics in core-shell heterostructures can be manipulated to achieve control over the reaction mechanism in photocatalysis.

Harvesting Hot Holes in Plasmon-Coupled Ultrathin Photoanodes for High-Performance Photoelectrochemical Water Splitting.

The harvesting of hot carriers produced by plasmon decay to generate electricity or drive a chemical reaction enables the reduction of the thermalization losses associated with supra-band gap photons in semiconductor photoelectrochemical (PEC) cells. Through the broadband harvesting of light, hot-carrier PEC devices also produce a sensitizing effect in heterojunctions with wide-band gap metal oxide semiconductors possessing good photostability and catalytic activity but poor absorption of visible wavelength photons. There are several reports of hot electrons in Au injected over the Schottky barrier into crystalline TiO2 and subsequently utilized to drive a chemical reaction but very few reports of hot hole harvesting. In this work, we demonstrate the efficient harvesting of hot holes in Au nanoparticles (Au NPs) covered with a thin layer of amorphous TiO2 (a-TiO2). Under AM1.5G 1 sun illumination, photoanodes consisting of a single layer of ∼50 nm diameter Au NPs coated with a 10 nm shell of a-TiO2 (Au@a-TiO2) generated 2.5 mA cm-2 of photocurrent in 1 M KOH under 0.6 V external bias, rising to 3.7 mA cm-2 in the presence of a hole scavenger (methanol). The quantum yield for hot-carrier-mediated photocurrent generation was estimated to be close to unity for high-energy photons (λ < 420 nm). Au@a-TiO2 photoelectrodes produced a small positive photocurrent of 0.1 mA cm-2 even at a bias of -0.6 V indicating extraction of hot holes even at a strong negative bias. These results together with density functional theory modeling and scanning Kelvin probe force microscope data indicate fast injection of hot holes from Au NPs into a-TiO2 and light harvesting performed near-exclusively by Au NPs. For comparison, Au NPs coated with a 10 nm shell of Al2O3 (Au@Al2O3) generated 0.02 mA cm-2 of photocurrent in 1 M KOH under 0.6 V external bias. These results underscore the critical role played by a-TiO2 in the extraction of holes in Au@a-TiO2 photoanodes, which is not replicated by an ordinary dielectric shell. It is also demonstrated here that an ultrathin photoanode (<100 nm in maximum thickness) can efficiently drive sunlight-driven water splitting.

COSMO-RS-Based Descriptors for the Machine Learning-Enabled Screening of Nucleotide Analogue Drugs against SARS-CoV-2.

Chemical similarity-based approaches employed to repurpose or develop new treatments for emerging diseases, such as COVID-19, correlates molecular structure-based descriptors of drugs with those of a physiological counterpart or clinical phenotype. We propose novel descriptors based on a COSMO-RS (short for conductor-like screening model for real solvents) σ-profiles for enhanced drug screening enabled by machine learning (ML). The descriptors' performance is hereby illustrated for nucleotide analogue drugs that inhibit the ribonucleic acid-dependent ribonucleic acid polymerase, key to viral transcription and genome replication. The COSMO-RS-based descriptors account for both chemical reactivity and structure, and are more effective for ML-based screening than fingerprints based on molecular structure and simple physical/chemical properties. The descriptors are evaluated using principal component analysis, an unsupervised ML technique. Our results correlate with the active monophosphate forms of the leading drug remdesivir and the prospective drug EIDD-2801 with nucleotides, followed by other promising drugs, and are superior to those from molecular structure-based descriptors and molecular docking. The COSMO-RS-based descriptors could help accelerate drug discovery for the treatment of emerging diseases.

Synthesis and Characterization of Zinc Phthalocyanine-Cellulose Nanocrystal (CNC) Conjugates: Toward Highly Functional CNCs.

We report highly fluorescent cellulose nanocrystals (CNCs) formed by conjugating a carboxylated zinc phthalocyanine (ZnPc) to two different types of CNCs. The conjugated nanocrystals (henceforth called ZnPc@CNCs) were bright green in color and exhibited absorption and emission maxima at ∼690 and ∼715 nm, respectively. The esterification protocol employed to covalently bind carboxylated ZnPc to surface hydroxyl group rich CNCs was expected to result in a monolayer of ZnPc on the surface of the CNCs. However, dynamic light scattering (DLS) studies indicated a large increase in the hydrodynamic radius of CNCs following conjugation to ZnPc, which suggests the binding of multiple ZnPc molecular layers on the CNC surface. This binding could be through co-facial π-stacking of ZnPc, where ZnPc metallophthalocyanine rings are horizontal to the CNC surface. The other possible binding mode would give rise to conjugated systems where ZnPc metallophthalocyanine rings are oriented vertically on the CNC surface. Density functional theory based calculations showed stable geometry following the conjugation protocol that involved covalently attached ester bond formation. The conjugates demonstrated superior performance for potential sensing applications through higher photoluminescence quenching capabilities compared to pristine ZnPc.

Consistently High Voc Values in p-i-n Type Perovskite Solar Cells Using Ni3+-Doped NiO Nanomesh as the Hole Transporting Layer.

Leading edge p-i-n type halide perovskite solar cells (PSCs) severely underperform n-i-p PSCs. p-i-n type PSCs that use PEDOT:PSS hole transport layers (HTLs) struggle to generate open-circuit photovoltage values higher than 1 V. NiO HTLs have shown greater promise in achieving high Voc values albeit inconsistently. In this report, a NiO nanomesh with Ni3+ defect grown by the hydrothermal method was used to obtain PSCs with Voc values that consistently exceeded 1.10 V (champion Voc = 1.14 V). A champion device photoconversion efficiency of 17.75% was observed. Density functional theory modeling was used to understand the interfacial properties of the NiO/perovskite interface. The PCE of PSCs constructed using the Ni3+-doped NiO nanomesh HTL was ∼34% higher than that of conventional compact NiO-based perovskite solar cells. A suite of characterization techniques such as transmission electron microscopy, field emission scanning electron microscopy, intensity-modulated photocurrent spectroscopy, intensity-modulated photovoltage spectroscopy, time-resolved photoluminescence, steady-state photoluminescence, and Kelvin probe force microscopy provided evidence of better film quality, enhanced charge transfer, and suppressed charge recombination in PSCs based on hydrothermally grown NiO nanostructures.

Multiscale methods framework: self-consistent coupling of molecular theory of solvation with quantum chemistry, molecular simulations, and dissipative particle dynamics.

In this work, we will address different aspects of self-consistent field coupling of computational chemistry methods at different time and length scales in modern materials and biomolecular science. Multiscale methods framework yields dramatically improved accuracy, efficiency, and applicability by coupling models and methods on different scales. This field benefits many areas of research and applications by providing fundamental understanding and predictions. It could also play a particular role in commercialization by guiding new developments and by allowing quick evaluation of prospective research projects. We employ molecular theory of solvation which allows us to accurately introduce the effect of the environment on complex nano-, macro-, and biomolecular systems. The uniqueness of this method is that it can be naturally coupled with the whole range of computational chemistry approaches, including QM, MM, and coarse graining.

A closure relation to molecular theory of solvation for macromolecules.

We propose a closure to the integral equations of molecular theory of solvation, particularly suitable for polar and charged macromolecules in electrolyte solution. This includes such systems as oligomeric polyelectrolytes at a finite concentration in aqueous and various non-aqueous solutions, as well as drug-like compounds in solution. The new closure by Kobryn, Gusarov, and Kovalenko (KGK closure) imposes the mean spherical approximation (MSA) almost everywhere in the solvation shell but levels out the density distribution function to zero (with the continuity at joint boundaries) inside the repulsive core and in the spatial regions of strong density depletion emerging due to molecular associative interactions. Similarly to MSA, the KGK closure reduces the problem to a linear equation for the direct correlation function which is predefined analytically on most of the solvation shells and has to be determined numerically on a relatively small (three-dimensional) domain of strong depletion, typically within the repulsive core. The KGK closure leads to the solvation free energy in the form of the Gaussian fluctuation (GF) functional. We first test the performance of the KGK closure coupled to the reference interaction site model (RISM) integral equations on the examples of Lennard-Jones liquids, polar and nonpolar molecular solvents, including water, and aqueous solutions of simple ions. The solvation structure, solvation chemical potential, and compressibility obtained from RISM with the KGK closure favorably compare to the results of the hypernetted chain (HNC) and Kovalenko-Hirata (KH) closures, including their combination with the GF solvation free energy. We then use the KGK closure coupled to RISM to obtain the solvation structure and thermodynamics of oligomeric polyelectrolytes and drug-like compounds at a finite concentration in electrolyte solution, for which no convergence is obtained with other closures. For comparison, we calculate their solvation structure from molecular dynamics (MD) simulations. We further couple the 3D-RISM integral equation with the 3D-version of the KGK closure, and solve it for molecular mixtures as well as oligomeric polyelectrolytes and drug-like molecules in electrolyte solutions.

The Effect of Molecular Structure and Environment on the Miscibility and Diffusivity in Polythiophene-Methanofullerene Bulk Heterojunctions: Theory and Modeling with the RISM Approach.

Although better means to model the properties of bulk heterojunction molecular blends are much needed in the field of organic optoelectronics, only a small subset of methods based on molecular dynamics- and Monte Carlo-based approaches have been hitherto employed to guide or replace empirical characterization and testing. Here, we present the first use of the integral equation theory of molecular liquids in modelling the structural properties of blends of phenyl-C61-butyric acid methyl ester (PCBM) with poly(3-hexylthiophene) (P3HT) and a carboxylated poly(3-butylthiophene) (P3BT), respectively. For this, we use the Reference Interaction Site Model (RISM) with the Universal Force Field (UFF) to compute the microscopic structure of blends and obtain insight into the miscibility of its components. Input parameters for RISM, such as optimized molecular geometries and charge distribution of interaction sites, are derived by the Density Functional Theory (DFT) methods. We also run Molecular Dynamics (MD) simulation to compare the diffusivity of the PCBM in binary blends with P3HT and P3BT, respectively. A remarkably good agreement with available experimental data and results of alternative modelling/simulation is observed for PCBM in the P3HT system. We interpret this as a step in the validation of the use of our approach for organic photovoltaics and support of its results for new systems that do not have reference data for comparison or calibration. In particular, for the less-studied P3BT, our results show that expectations about its performance in binary blends with PCBM may be overestimated, as it does not demonstrate the required level of miscibility and short-range structural organization. In addition, the simulated mobility of PCBM in P3BT is somewhat higher than what is expected for polymer blends and falls into a range typical for fluids. The significance of our predictive multi-scale modelling lies in the insights it offers into nanoscale morphology and charge transport behaviour in multi-component organic semiconductor blends.

Supramolecular Interactions in Secondary Plant Cell Walls: Effect of Lignin Chemical Composition Revealed with the Molecular Theory of Solvation.

Plant biomass recalcitrance, a major obstacle to achieving sustainable production of second generation biofuels, arises mainly from the amorphous cell-wall matrix containing lignin and hemicellulose assembled into a complex supramolecular network that coats the cellulose fibrils. We employed the statistical-mechanical, 3D reference interaction site model with the Kovalenko-Hirata closure approximation (or 3D-RISM-KH molecular theory of solvation) to reveal the supramolecular interactions in this network and provide molecular-level insight into the effective lignin-lignin and lignin-hemicellulose thermodynamic interactions. We found that such interactions are hydrophobic and entropy-driven, and arise from the expelling of water from the mutual interaction surfaces. The molecular origin of these interactions is carbohydrate-π and π-π stacking forces, whose strengths are dependent on the lignin chemical composition. Methoxy substituents in the phenyl groups of lignin promote substantial entropic stabilization of the ligno-hemicellulosic matrix. Our results provide a detailed molecular view of the fundamental interactions within the secondary plant cell walls that lead to recalcitrance.

Electric Interfacial Layer of Modified Cellulose Nanocrystals in Aqueous Electrolyte Solution: Predictions by the Molecular Theory of Solvation.

The X-ray crystal structure-based models of Iα cellulose nanocrystals (CNC), both pristine and containing surface sulfate groups with negative charge 0-0.34 e/nm(2) produced by sulfuric acid hydrolysis of softwood pulp, feature a highly polarized "crystal-like" charge distribution. We perform sampling using molecular dynamics (MD) of the structural relaxation of neutral pristine and negatively charged sulfated CNC of various lengths in explicit water solvent and then employ the statistical mechanical 3D-RISM-KH molecular theory of solvation to evaluate the solvation structure and thermodynamics of the relaxed CNC in ambient aqueous NaCl solution at a concentration of 0.0-0.25 mol/kg. The MD sampling induces a right-hand twist in CNC and rearranges its initially ordered structure with a macrodipole of high-density charges at the opposite faces into small local spots of alternating charge at each face. This surface charge rearrangement observed for both neutral and charged CNC significantly affects the distribution of ions around CNC in aqueous electrolyte solution. The solvation free energy (SFE) of charged sulfated CNC has a minimum at a particular electrolyte concentration depending on the surface charge density, whereas the SFE of neutral CNC increases linearly with NaCl concentration. The SFE contribution from Na(+) counterions exhibits behavior similar to the NaCl concentration dependence of the whole SFE. An analysis of the 3D maps of Na(+) density distributions shows that these model CNC particles exhibit the behavior of charged nanocolloids in aqueous electrolyte solution: an increase in electrolyte concentration shrinks the electric interfacial layer and weakens the effective repulsion between charged CNC particles. The 3D-RISM-KH method readily treats solvent and electrolyte of a given nature and concentration to predict effective interactions between CNC particles in electrolyte solution. We provide CNC structural models and a modeling procedure for studies of effective interactions and the formation of ordered phases of CNC suspensions in electrolyte solution.

Donor-acceptor small molecules for organic photovoltaics: single-atom substitution (Se or S).

Two isostructural low-band-gap small molecules that contain a one-atom substitution, S for Se, were designed and synthesized. The molecule 7,7'-[4,8-bis(2-ethylhexyloxy)benzo[1,2-b:4,5-b']dithiophene]bis[6-fluoro-4-(5'-hexyl-2,2'-bithiophen-5-yl)benzo[c][1,2,5]thiadiazole] (1) and its selenium analogue 7,7'-[4,8-bis(2-ethylhexyloxy)benzo[1,2-b:4,5-b']dithiophene]bis[6-fluoro-4-(5'-hexyl-2,2'-bithiophen-5-yl)benzo[c][1,2,5]selenodiazole] (2) are both based on the electron-rich central unit benzo[1,2-b:4,5-b']dithiophene. The aim of this work was to investigate the effect of one-atom substitution on the optoelectronic properties and photovoltaic performance of devices. Theoretical calculations revealed that this one-atom variation has a small but measurable effect on the energy of frontier molecular orbital (HOMO and LUMO), which, in turn, can affect the absorption profile of the molecules, both neat and when mixed in a bulk heterojunction (BHJ) with PC71BM. The Se-containing variant 2 led to higher efficiencies [highest power conversion efficiency (PCE) of 2.6%] in a standard organic photovoltaic architecture, when combined with PC71BM after a brief thermal annealing, than the S-containing molecule 1 (highest PCE of 1.0%). Studies of the resulting morphologies of BHJs based on 1 and 2 showed that one-atom substitution could engender important differences in the solubilities, which then influenced the crystal orientations of the small molecules within this thin layer. Brief thermal annealing resulted in rotation of the crystalline grains of both molecules to more energetically favorable configurations.

Dissipative particle dynamics with an effective pair potential from integral equation theory of molecular liquids.

We present a method of DPD simulation based on a coarse-grained effective pair potential obtained from the DRISM-KH molecular theory of solvation. The theory is first used to calculate the radial distribution functions of all-atom solute monomers in all-atom solvent and then to invert them into an effective pair potential between coarse-grained beads such that their fluid without solvent accounts for molecular specificities and solvation effects in the all-atom system. Bonded interactions are sampled in relatively short MD of the all-atom system and modeled with best multi-Gaussian fit. Replacing the heuristically defined conservative force potential in DPD, the coarse-grained effective pair potential is free from the artificial restrictions on potential range and shape and on equal volume of solute and solvent blobs inherent in standard DPD. The procedure is flexible in specifying coarse-grained mapping and enormously increases computational efficiency by eliminating solvent. The method is validated on polystyrene chains of various length in toluene at finite concentrations for room and polystyrene glass transition temperature. It yields the chain elastic properties and diffusion coefficient in good agreement with experiment and all-atom MD simulations. DPD with coarse-grained effective pair potential is capable of predicting both structural and dynamic properties of polymer solutions and soft matter with high accuracy and computational efficiency.

Computational study of the effect of dispersion interactions on the thermochemistry of aggregation of fused polycyclic aromatic hydrocarbons as model asphaltene compounds in solution.

Density functional theory (DFT), Møller-Plesset second-order perturbation theory (MP2), and semiempirical methods are employed for the geometry optimization and thermochemistry analysis of π-π stacked di-, tri-, tetra-, and pentamer aggregates of the fused polycyclic aromatic hydrocarbons (PAHs) naphthalene, anthracene, phenanthrene, tetracene, pyrene, and coronene as well as benzene. These aggregates (stabilized by dispersion interactions) are highly relevant to the intermolecular aggregation of asphaltenes, major components of heavy petroleum. The strength of π-π stacking interaction is evaluated with respect to the π-stacking distance and thermochemistry results, such as aggregation enthalpies, entropies, and Gibbs free energies (ΔG(298)). For both π-stacking interplanar distances and thermochemistry, the ωB97X-D functional with an augmented damped R(-6) dispersion correction term and MP2 are in the closest agreement with the highly accurate spin-component scaled MP2 (SCS-MP2) method that we selected as a reference. The ΔG(298) values indicate that the aggregation of coronene is spontaneous at 298 K and the formation of pyrene dimers occurs spontaneously at temperature lower than 250 K. Aggregates of smaller PAHs would be stable at even lower temperature. These findings are supported by X-ray crystallographic determination results showing that among the PAHs studied only coronene forms continuous stacked aggregates in single crystals, pyrene forms dimers, and smaller PAHs do not form π-π stacked aggregates. Thermochemistry analysis results show that PAHs containing more than four fused benzene rings would spontaneously form aggregates at 298 K. Also, round-shaped PAHs, such as phenanthrene and pyrene, form more stable aggregates than linear PAHs, such as anthracene and tetracene, due to decreased entropic penalty. These results are intended to help guide the synthesis of model asphaltene compounds for spectroscopic studies so as to help understand the aggregation behavior of heavy petroleum.