Identification of Unknown Inverted Singlet-Triplet Cores by High-Throughput Virtual Screening.

Molecules where the energy of the lowest excited singlet state is found below the energy of the lowest triplet state (inverted singlet-triplet molecules) are extremely rare. It is particularly challenging to discover new ones through virtual screening because the required wavefunction-based methods are expensive and unsuitable for high-throughput calculations. Here, we devised a virtual screening approach where the molecules to be considered with advanced methods are pre-selected with increasingly more sophisticated filters that include the evaluation of the HOMO-LUMO exchange integral and approximate CASSCF calculations. A final set of 7 candidates (0.05% of the initial 15 000) were verified to possess inversion between singlet and triplet states with state-of-the-art multireference methods (MS-CASPT2). One of them is deemed of particular interest because it is unrelated to other proposals made in the literature.

Efficient Electronic Tunneling Governs Transport in Conducting Polymer-Insulator Blends.

Electronic transport models for conducting polymers (CPs) and blends focus on the arrangement of conjugated chains, while the contributions of the nominally insulating components to transport are largely ignored. In this work, an archetypal CP blend is used to demonstrate that the chemical structure of the non-conductive component has a substantial effect on charge carrier mobility. Upon diluting a CP with excess insulator, blends with as high as 97.4 wt % insulator can display carrier mobilities comparable to some pure CPs such as polyaniline and low regioregularity P3HT. In this work, we develop a single, multiscale transport model based on the microstructure of the CP blends, which describes the transport properties for all dilutions tested. The results show that the high carrier mobility of primarily insulator blends results from the inclusion of aromatic rings, which facilitate long-range tunneling (up to ca. 3 nm) between isolated CP chains. This tunneling mechanism calls into question the current paradigm used to design CPs, where the solubilizing or ionically conducting component is considered electronically inert. Indeed, optimizing the participation of the nominally insulating component in electronic transport may lead to enhanced electronic mobility and overall better performance in CPs.

Rapid calculation of internal conversion and intersystem crossing rate for organic materials discovery.

The internal conversion (IC) process from S1 to S0 and the intersystem crossing (ISC) transition from T1 to S0 are two essential processes in functional molecular material design. Despite their importance, it is currently impossible to evaluate the rate of these processes for a large set of molecules and, therefore, perform high-throughput virtual screening in large-scale data to gain more physical insight. In this work, we explore possible approaches to accelerate the calculations of IC and ISC rates based on a systematic reduction of the number of modes included in the computation and the study of the importance of the different parameters and the influence of their accuracy on the final result. The results reproduce the experimental trends with systematic errors that are ultimately due to the approximations of the theory. We noted that plausible results for ISC in planar molecules are only obtained by including the effect of Hertzberg-Teller coupling. Our method establishes the feasibility and expected accuracy of the computation of nonradiative rates in the virtual screening of molecular materials.

Determining usefulness of machine learning in materials discovery using simulated research landscapes.

When existing experimental data are combined with machine learning (ML) to predict the performance of new materials, the data acquisition bias determines ML usefulness and the prediction accuracy. In this context, the following two conditions are highly common: (i) constructing new unbiased data sets is too expensive and the global knowledge effectively does not change by performing a limited number of novel measurements; (ii) the performance of the material depends on a limited number of physical parameters, much smaller than the range of variables that can be changed, albeit such parameters are unknown or not measurable. To determine the usefulness of ML under these conditions, we introduce the concept of simulated research landscapes, which describe how datasets of arbitrary complexity evolve over time. Simulated research landscapes allow us to use different discovery strategies to compare standard materials exploration with ML-guided explorations, i.e. we can measure quantitatively the benefit of using a specific ML model. We show that there is a window of opportunity to obtain a significant benefit from ML-guided strategies. The adoption of ML can take place too soon (not enough information to find patterns) or too late (dense datasets only allow for negligible ML benefit), and the adoption of ML can even slow down the discovery process in some cases. We offer a qualitative guide on when ML can accelerate the discovery of new best-performing materials in a field under specific conditions. The answer in each case depends on factors like data dimensionality, corrugation and data collection strategy. We consider how these factors may affect the ML prediction capabilities and discuss some general trends.

Local structuring of diketopyrrolopyrrole (DPP)-based oligomers from molecular dynamics simulations.

The microscopic structure of high mobility semiconducting polymers is known to be essential for their performance but it cannot be easily deduced from the available experimental data. A series of short oligomers of diketopyrrolopyrrole (DPP)-based materials that display high charge mobility are studied by molecular dynamics simulations to understand their local structuring at an atomic level. Different analyses are proposed to compare the ability of different oligomers to form large aggregates and their driving force. The simulations show that the tendency for this class of materials to form aggregates is driven by the interaction between DPP fragments, but this is modulated by the other conjugated fragments of the materials which affect the rigidity of the polymer and, ultimately, the size of the aggregates that are formed. The main structural features and the electronic structure of the oligomers are fairly similar above the glass transition temperature and at room temperature.

Modeling charge transport in high-mobility molecular semiconductors: Balancing electronic structure and quantum dynamics methods with the help of experiments.

Computing the charge mobility of molecular semiconductors requires a balanced set of approximations covering both the electronic structure of the Hamiltonian parameters and the modeling of the charge dynamics. For problems of such complexity, it is hard to make progress without independently validating each layer of approximation. In this perspective, we survey how all terms of the model Hamiltonian can be computed and validated by independent experiments and discuss whether some common approximations made to build the model Hamiltonian are valid. We then consider the range of quantum dynamics approaches used to model the charge carrier dynamics stressing the strong and weak points of each method on the basis of the available computational results. Finally, we discuss non-trivial aspects and novel opportunities related to the comparison of theoretical predictions with recent experimental data.

Serum concentrations of leptin in pregnant and non-pregnant bitches.

Leptin regulates body weight and several physiological processes including reproduction. We evaluated the circulating levels of leptin in pregnant and non-pregnant bitches as well as their correlation with body weight, food intake and number of foetuses. Nineteen healthy German shepherd bitches were used and divided in two groups (pregnant n = 12 and non-pregnant n = 7). Blood samples were collected every 15 days starting from ovulation (Day 0) throughout pregnancy (pregnant group, P) or throughout luteal phase (non-pregnant group, NP) In pregnant bitches, leptin concentrations increased from the day of ovulation (1.32 ± 0.06 ng/ml) up to day 45 (1.51 ± 0.06 ng/ml; p < .01) and returned to baseline values from day 60 post-ovulation. In non-pregnant bitches, leptin concentrations remained constant throughout the whole observation period (estimated marginal mean ± SE=1.33 ± 0.38 ng/ml). Pairwise comparisons showed significant differences between P and NP at day 45 post-ovulation (p < .05). Multivariable models indicated that, controlling for time and litter size, there was a positive relationship between leptin concentration and BW (p < .05) although Pearson coefficients showed that the correlation between BW and leptin was only significant in NP animals at day 45 (r = 0.76, p < .05). The multivariable approach also suggested that, holding BW and time constant, leptin concentrations tend to increase as the number of puppies increased (p = .06). Our study supports indirectly the contribution of the feto-placental unit to the circulating maternal leptin concentration.

Effect of aglepristone (RU534) administration during follicular phase on progesterone, estradiol-17ß and LH serum concentrations in bitches.

Aglepristone was administered in bitches during the follicular phase to evaluate its effects on progesterone, estradiol-17ß and LH serum concentrations. Ten German Shepherds were divided into two groups (treated n = 5; control n = 5). Treated bitches received 10 mg/kg BW of aglepristone subcutaneously during the early follicular phase, 24 hr after and then 7 days later. The control group was injected, at the same time periods, with saline solution (0.3 ml/kg BW). For the steroid evaluations, blood was collected daily from the onset of proestrus until the first day of cytological dioestrus. For LH base-line serum determination, blood was also collected every 20 min for 2 hr at the onset of proestrus. For LH surge identification, blood was collected daily (every 6 hr) starting from the day of the first administration of aglepristone or saline solution until the first day of dioestrus. All animals ovulated but the treated group presented longer ovulation-dioestrus intervals than the control group (5.2 ± 2.2 days p < .05). Serum concentrations of the evaluated hormones were similar between experimental animals except for serum LH. Indeed, no LH peaks were detected in the treated group while LH surges were clearly observed in the control group (9 ± 1 days after the beginning of proestrus. In particular, the area under the curve for LH was significantly lower in treated than control animals (12 ± 4 ng/ml x Day; p = .01). In conclusion, administrations of aglepristone during the follicular phase of the bitch does not affect the steroid hormone patterns but does prevent the occurrence of a LH surge. This work raises significant questions and opens perspectives concerning the mechanisms of ovulation in bitches.

On the arrangement of chromophores in light harvesting complexes: chance versus design.

We used a homogeneous computational approach to derive the excitonic Hamiltonian for five light harvesting complexes containing only one type of chromophore and compare them in terms of statistical descriptors. We then studied the approximate exciton dynamics for the five complexes introducing a measure, the (averaged and time-dependent) inverse participation ratio, that enables the comparison between very diverse complexes on the same ground. We find that the global dynamics are very similar across the set of systems despite the variety of geometric structures of the complexes. In particular, the dynamics of four out of five light harvesting complexes are barely distinguishable with a small variation from the norm seen only for the Fenna-Matthews-Olson complex. We use the information from the realistic Hamiltonians to build a reduced model system that shows how the global dynamics are ultimately dominated by a single parameter, the degree of localization of the excitonic Hamiltonian eigenstates. Considering the physically plausible range of system parameters, the reduced model explains why the dynamics are so similar across most light harvesting complexes containing a single type of chromophore regardless of the detailed pattern of the inter-chromophore excitonic coupling.

Intra-ovarian dynamic blood flow in pseudopregnant rabbits during prostaglandin F2α-induced luteolysis.

In the present study, we evaluated the dynamic changes of intra-ovarian blood flow, by real-time colour-coded and pulsed Doppler ultrasonography, as well as the immunopresence of prostaglandin F2α (PGF2α) receptor (FP) and peripheral plasma progesterone concentrations in pseudopregnant rabbit after PGF2α treatments at either early- (4 days) and mid-luteal (9 days) stages. During the pre-treatment observation interval of one hour, the ovarian blood flows showed a fluctuating pattern. Independently of luteal stage, PGF2α administration caused a fourfold decline in the blood flow within 40 min that was followed 50 min later by a reactive hyperaemia that lasted several hours, while the resistive index showed an opposite trend. Twenty-four hour later, the blood flow was one half that measured before PGF2α injection. At day 4 of pseudopregnancy, PGF2α did not affect peripheral plasma progesterone concentrations, but at day 9, it caused functional luteolysis as progesterone levels declined 6 hr later to reach basal values after 24 hr. The changes in the ovarian blood flows of pseudopregnant rabbits receiving PGF2α were accompanied by simultaneous changes in the resistance index. This biphasic response in the blood flow and vascular resistances likely reflects reactive hyperaemia following vasoconstriction. By immunohistochemistry, strong positive immune reaction for FP was detected in the cytoplasm of endothelial cells of ovarian arteries, veins and capillaries. In conclusion, these results suggest that PGF2α could acutely regulate the ovarian blood flow of pseudopregnant rabbits, even if there is no evidence of a blood flow reduction anticipating luteolysis.

How fine-tuned for energy transfer is the environmental noise produced by proteins around biological chromophores?

We investigate the role of the local protein environment on the energy transfer processes in biological molecules, excluding from the analysis the effect of intra-chromophore nuclear motions, and focussing on the exciton-phonon coupling. We studied three different proteins (FMO and two variants of the WSCP protein) with different biological functions but similar chromophores, to understand whether a classification of chromophores based on the details of the environment would be possible, and whether specific environments enhance or suppress the coupling between exciton and protein dynamics. Our results show that despite the different biological role, there is no significant difference in the influence of the environment on the properties of the chromophores. Additionally, we show that the main role in influencing molecular properties is played by solvent molecules: the interaction occurs on a medium-range scale, and the solvent is kept in place by a strong H-bond network being free to rotate, suggesting a dipole-dipole interaction mechanism. Steric hindrance exerted by other moieties can help modulating the interactions and tuning the energy transfer process. Overall, considering also the relatively greater importance of intra-molecular nuclear motions, the protein environment around biological chromophores does not appear fine-tuned for a specific function.

Doppler evaluation of umbilical artery during normal gestation in sheep.

Throughout gestation, changes in foetal umbilical cord Doppler parameters in ewes were detected. Doppler ultrasonography of the umbilical artery was performed weekly starting at 18 weeks before parturition until birth. In the foetal umbilical artery (UA), systolic peak velocity (SPV), end diastolic velocity (EDV), increased (p for within-subjects effect <0.001) while pulsatility index (PI) resistance index (RI) decreased (p for within-subjects effect <0.001) with the progress of pregnancy. A linear trend was found on all patterns (p < 0.001). In particular, the EDV values increased significantly (p < 0.05) with respect to previous weeks, at weeks 16, 11, 10, 7, and 1 before parturition. The SPV values increased significantly (p < 0.05), with respect to previous observations, at weeks 11, 10, and 7 before parturition. Finally, the PI and RI decreased significantly (p < 0.05) only at week 7 before parturition. The increased velocities and reduced resistance index suggest a progressive increment in blood flow to the foetus towards the end of pregnancy. Foetal and utero-placental vascular parameters can be reliably evaluated using high-frequency ultrasound.

How Many Parameters Actually Affect the Mobility of Conjugated Polymers?

We describe charge transport along a polymer chain with a generic theoretical model depending in principle on tens of parameters, reflecting the chemistry of the material. The charge carrier states are obtained from a model Hamiltonian that incorporates different types of disorder and electronic structure (e.g., the difference between homo- and copolymer). The hopping rate between these states is described with a general rate expression, which contains the rates most used in the literature as special cases. We demonstrate that the steady state charge mobility in the limit of low charge density and low field ultimately depends on only two parameters: an effective structural disorder and an effective electron-phonon coupling, weighted by the size of the monomer. The results support the experimental observation [N. I. Craciun, J. Wildeman, and P. W. M. Blom, Phys. Rev. Lett. 100, 056601 (2008)PRLTAO0031-900710.1103/PhysRevLett.100.056601] that the mobility in a broad range of (polymeric) semiconductors follows a universal behavior, insensitive to the chemical detail.

Vibronic enhancement of excitation energy transport: Interplay between local and non-local exciton-phonon interactions.

It has been reported in recent years that vibronic resonance between vibrational energy of the intramolecular nuclear mode and excitation-energy difference is crucial to enhance excitation energy transport in light harvesting proteins. Here we investigate how vibronic enhancement induced by vibronic resonance is influenced by the details of local and non-local exciton-phonon interactions. We study a heterodimer model with parameters relevant to the light-harvesting proteins with the surrogate Hamiltonian quantum dynamics method in a vibronic basis. In addition, the impact of field-driven excitation on the efficiency of population transfer is compared with the instantaneous excitation, and the effect of multi-mode vibronic coupling is presented in comparison with the coupling to a single effective vibrational mode. We find that vibronic enhancement of site population transfer is strongly suppressed with the increase of non-local exciton-phonon interaction and increasing the number of strongly coupled high-frequency vibrational modes leads to a further decrease in vibronic enhancement. Our results indicate that vibronic enhancement is present but may be much smaller than previously thought and therefore care needs to be taken when interpreting its role in excitation energy transport. Our results also suggest that non-local exciton-phonon coupling, which is related to the fluctuation of the excitonic coupling, may be as important as local exciton-phonon coupling and should be included in any quantum dynamics model.

A computational study of the competing reaction mechanisms of the photo-catalytic reduction of CO2 on anatase(101).

We perform a computational study of three different reaction mechanisms for the photo-catalytic reduction of CO2 on the TiO2 anatase(101) surface known as (i) the carbene, (ii) the formaldehyde and (iii) the glyoxal pathways. We define a set of approximations that allows testing a number of mechanistic hypotheses and design experiments to validate them. We find that the energetically most favourable reaction mechanism among those proposed in the literature is the formaldehyde path, and the rate-limiting step is likely to be the formation of CH3 radicals from dissociation of CH3OH. We show that an intermediate that supports this mechanism is OCH2OH. We also find that formaldehyde would be an energetically favorable intermediate forming from CO and HCO, intermediates that are proposed in the early stage of the carbene and glyoxal pathways respectively. Some possible variants of mechanisms and methods to ease the formation of CH3 radicals are also discussed.

Quantum dynamics of a vibronically coupled linear chain using a surrogate Hamiltonian approach.

Vibronic coupling between the electronic and vibrational degrees of freedom has been reported to play an important role in charge and exciton transport in organic photovoltaic materials, molecular aggregates, and light-harvesting complexes. Explicitly accounting for effective vibrational modes rather than treating them as a thermal environment has been shown to be crucial to describe the effect of vibronic coupling. We present a methodology to study dissipative quantum dynamics of vibronically coupled systems based on a surrogate Hamiltonian approach, which is in principle not limited by Markov approximation or weak system-bath interaction, using a vibronic basis. We apply vibronic surrogate Hamiltonian method to a linear chain system and discuss how different types of relaxation process, intramolecular vibrational relaxation and intermolecular vibronic relaxation, influence population dynamics of dissipative vibronic systems.

Dynamics of the excitonic coupling in organic crystals.

We show that the excitonic coupling in molecular crystals undergoes a very large fluctuation at room temperature as a result of the combined thermal motions of the nuclei. This observation dramatically affects the description of exciton transport in organic crystals and any other phenomenon (like singlet fission or exciton dissociation) that originates from an exciton in a molecular crystal or thin film. This unexpected result is due to the predominance of the short-range excitonic coupling mechanisms (exchange, overlap, and charge-transfer mediated) over the Coulombic excitonic coupling for molecules in van der Waals contact. To quantify this effect we develop a procedure to evaluate accurately the short-range excitonic coupling (via a diabatization scheme) along a molecular dynamics trajectory of the representative molecular crystals of anthracene and tetracene.

Developing accurate molecular mechanics force fields for conjugated molecular systems.

A rapid method to parameterize the intramolecular component of classical force fields for complex conjugated molecules is proposed. The method is based on a procedure of force matching with a reference electronic structure calculation. It is particularly suitable for those applications where molecular dynamics simulations are used to generate structures that are therefore analysed by electronic structure methods, because it is possible to build force fields that are consistent with electronic structure calculations that follow classical simulations. Such applications are commonly encountered in organic electronics, spectroscopy of complex systems and photobiology (e.g. photosynthetic systems). We illustrate the method by parameterizing the force fields of a molecule used in molecular semiconductors (2,2-dicyanovinyl-capped S,N-heteropentacene or DCV-SN5), a polymeric semiconductor (thieno[3,2-b]thiophene-diketopyrrolopyrrole TT-DPP) and a chromophore embedded in a protein environment (15,16-dihydrobiliverdin or DBV) where several hundreds of parameters need to be optimized in parallel.

Excitonic couplings between molecular crystal pairs by a multistate approximation.

In this paper, we present a diabatization scheme to compute the excitonic couplings between an arbitrary number of states in molecular pairs. The method is based on an algebraic procedure to find the diabatic states with a desired property as close as possible to that of some reference states. In common with other diabatization schemes, this method captures the physics of the important short-range contributions (exchange, overlap, and charge-transfer mediated terms) but it becomes particularly suitable in presence of more than two states of interest. The method is formulated to be usable with any level of electronic structure calculations and to diabatize different types of states by selecting different molecular properties. These features make the diabatization scheme presented here especially appropriate in the context of organic crystals, where several excitons localized on the same molecular pair may be found close in energy. In this paper, the method is validated on the tetracene crystal dimer, a well characterized case where the charge transfer (CT) states are closer in energy to the Frenkel excitons (FE). The test system was studied as a function of an external electric field (to explore the effect of changing the relative energy of the CT excited state) and as a function of different intermolecular distances (to probe the strength of the coupling between FE and CT states). Additionally, we illustrate how the approximation can be used to include the environment polarization effect.

A very general rate expression for charge hopping in semiconducting polymers.

We propose an expression of the hopping rate between localized states in semiconducting disordered polymers that contain the most used rates in the literature as special cases. We stress that these rates cannot be obtained directly from electron transfer rate theories as it is not possible to define diabatic localized states if the localization is caused by disorder, as in most polymers, rather than nuclear polarization effects. After defining the separate classes of accepting and inducing nuclear modes in the system, we obtain a general expression of the hopping rate. We show that, under the appropriate limits, this expression reduces to (i) a single-phonon rate expression or (ii) the Miller-Abrahams rate or (iii) a multi-phonon expression. The description of these limits from a more general expression is useful to interpolate between them, to validate the assumptions of each limiting case, and to define the simplest rate expression that still captures the main features of the charge transport. When the rate expression is fed with a range of realistic parameters the deviation from the Miller-Abrahams rate is large or extremely large, especially for hopping toward lower energy states, due to the energy gap law.