Enhancing Singlet Fission Coupling with Nonbonding Orbitals.

Singlet fission (SF) is a process where a singlet exciton is split into a pair of triplet excitons. The increase in the excitonic generation can be exploited to enhance the efficiency of solar cells. Molecules with conjugated π bonds are commonly developed for optoelectronic applications including SF, due to their low energy gaps. The electronic coupling for SF in such well-stacked π-conjugated molecule pairs can be rather limited due to the orthogonal π and π* orbital overlaps that are involved in the coupling elements, leading to a large cancellation in the coupling. In the present work, we show that such limits can be removed by involving triplet states of different origins, such as those with nonbonding n orbitals. We demonstrate such an effect for formaldehyde and methylenimine dimers, with a low-lying n-π* triplet state (T1) in addition to the π-π* triplet (T2). We show that the coupling can be enhanced by 40 times or more for the formaldehyde dimer, and 15 times or more for the methylenimine dimer, with the T1-T2 state as the end product of SF. With 1759 randomly oriented pairs of formaldehyde derived from a molecular dynamics simulation, the coupling from a singlet exciton to this T1-T2 state is, on an average, almost two times larger than that for a regular T1-T1 state. We investigated a few families that have been shown to be prospective candidates for SF, using our proposed strategy. However, our unfavorable results indicate that there are clear difficulties in fulfilling the ES1 ≳ ET1 + ET2 energy criterion. Nevertheless, our results provide a new molecular design concept for better SF (and triplet-triplet annihilation, TTA) materials that allows future development.

Molecular dynamics simulations of two double-helical hexamer fragments of iota-carrageenan in aqueous solution.

The gelation of anionic carrageenans is known to occur through a coil-to-helix transition followed by further aggregation or association on which positive counterions play a significant role. In the present work, molecular dynamics (MD) simulations were performed on two double-helical iota-carrageenan hexamer fragments along with their sodium counterions using the Carbohydrate Solution Force Field (CSFF) in an aqueous (TIP4P) solution with the GROMACS molecular dynamics package. Results showed a counterion condensation between the two double helices and that the subsequent forces of interaction between them were predominantly attractive. By varying the distance separating the two double helices, the effect of distance on the counterion distribution and the forces of attraction was also investigated. In the presence of counterions, an increase in the forces of attraction was observed as the distance between the two double helices decreases which can be attributed to the greater counterion density between the two like-charged oligosaccharides.

Structural Dynamics of Neighboring Water Molecules of N-Isopropylacrylamide Pentamer.

Poly(N-isopropylacrylamide) (PNIPAM) is a popular polymer widely used in smart hydrogel synthesis due to its thermo-responsive behavior in aqueous medium. Aqueous PNIPAM hydrogels can reversibly swell and collapse below and above their lower critical solution temperature (LCST), respectively. The present work used molecular dynamics simulations to explore the behavior of water molecules surrounding the side chains of a NIPAM pentamer in response to temperature changes (273-353 K range) near its experimental LCST (305 K). Results suggest a strong inverse correlation of temperature with water density and hydrophobic hydration character of the first coordination shell around the isopropyl groups. Integrity of the first and second coordination shells is further characterized by polygon ring analysis. Predominant occurrence of pentagons suggests clathrate-like behavior of both shells at lower temperatures. This predominance is eventually overtaken by 4-membered rings as temperature is increased beyond 303 and 293 K for the first and second coordination shells, respectively, losing their clathrate-like property. It is surmised that this temperature-dependent stability of the coordination shells is one of the important factors that controls the reversible swell-collapse mechanism of PNIPAM hydrogels.

Machine Learning for Predicting Electron Transfer Coupling.

Electron transfer coupling is a critical factor in determining electron transfer rates. This coupling strength can be sensitive to details in molecular geometries, especially intermolecular configurations. Thus, studying charge transporting behavior with a full first-principle approach demands a large amount of computation resources in quantum chemistry (QC) calculation. To address this issue, we developed a machine learning (ML) approach to evaluate electronic coupling. A prototypical ML model for an ethylene system was built by kernel ridge regression with Coulomb matrix representation. Since the performance of the ML models highly dependent on their building strategies, we systematically investigated the generality of the ML models, the choice of features and target labels. The best ML model trained with 40 000 samples achieved a mean absolute error of 3.5 meV and greater than 98% accuracy in predicting phases. The distance and orientation dependence of electronic coupling was successfully captured. Bypassing QC calculation, the ML model saved 10-104 times the computation cost. With the help of ML, reliable charge transport models and mechanisms can be further developed.

First Principle Prediction of Intramolecular Singlet Fission and Triplet Triplet Annihilation Rates.

Intramolecular singlet fission and triplet-triplet annihilation (TTA) has been experimentally observed and reported. However, problems remain in theoretically accounting for the corresponding intramolecular electronic couplings and their rates. We used the fragment excitation difference (FED) scheme to calculate the coupling with states from restricted active-space spin-flip configuration interaction. We investigated three covalently linked pentacene dimers via a phenyl group in an ortho-, meta-, and para-arrangement. The singlet fission and TTA couplings were enhanced when two chromophores were covalently linked. With the Fermi golden rule, both the estimated singlet fission and TTA rates were in line with the experimental results. For systems with significant singlet-fission coupling, charge-transfer components were observed in the excited states involved, and charge-transfer states were also seen within 1 eV above the singlet excited states. Our approach allows for an analysis of through-bond versus through-space singlet fission in the full electronic wave functions. The FED scheme is useful for calculating intramolecular singlet-fission and TTA couplings.

Hamiltonian-Independent Generalization of the Fragment Excitation Difference Scheme.

The fragment excitation difference (FED) scheme is a useful method for calculating the complete diabatic couplings of various energy transfer systems. The lack of a good definition for the transformation of the transition density matrix to the off-diagonal FED matrix elements limits FED to single-excitation methods. We have developed a generalized FED scheme called the θ-optimized FED (θ-FED) scheme which does not require transforming the transition density matrices. In θ-FED, two states of interest are linearly transformed by a mixing angle θ into two mixed states. The excitation difference of each mixed state is evaluated and optimized numerically to determine the mixing angle. This approach allows for finding diabatic states and the corresponding couplings for a general set of Hamiltonians.

Comparison of a hydrogel model to the Poisson-Boltzmann cell model.

We have investigated a single charged microgel in aqueous solution with a combined simulational model and Poisson-Boltzmann theory. In the simulations we use a coarse-grained charged bead-spring model in a dielectric continuum, with explicit counterions and full electrostatic interactions under periodic and nonperiodic boundary conditions. The Poisson-Boltzmann hydrogel model is that of a single charged colloid confined to a spherical cell where the counterions are allowed to enter the uniformly charged sphere. In order to investigate the origin of the differences these two models may give, we performed a variety of simulations of different hydrogel models which were designed to test for the influence of charge correlations, excluded volume interactions, arrangement of charges along the polymer chains, and thermal fluctuations in the chains of the gel. These intermediate models systematically allow us to connect the Poisson-Boltzmann cell model to the bead-spring model hydrogel model in a stepwise manner thereby testing various approximations. Overall, the simulational results of all these hydrogel models are in good agreement, especially for the number of confined counterions within the gel. Our results support the applicability of the Poisson-Boltzmann cell model to study ionic properties of hydrogels under dilute conditions.