Static Energy Disorder Research Articles

The influence of sorbitol doping on aggregation and electronic properties of PEDOT:PSS: a theoretical study

Many organic electronics applications such as organic solar cells or thermoelectric generators rely on PEDOT:PSS as a conductive polymer that is printable and transparent. It was found that doping PEDOT:PSS with sorbitol enhances the conductivity through morphological changes. However, the microscopic mechanism is not well understood. In this work, we combine computational tools with machine learning to investigate changes in morphological and electronic properties of PEDOT:PSS when doped with sorbitol. We find that sorbitol improves the alignment of PEDOT oligomers, leading to a reduction of energy disorder and an increase in electronic couplings between PEDOT chains. The high accuracy (r 2 > 0.9) and speed up of energy level predictions of neural networks compared to density functional theory enables us to analyze HOMO energies of PEDOT oligomers as a function of time. We find a surprisingly low degree of static energy disorder compared to other organic semiconductors. This finding might help to better understand the microscopic origin of the high charge carrier mobility of PEDOT:PSS in general and potentially help to design new conductive polymers.

Significantly Reduced Thermal-Activation Energy for Hole Transport via Simple Donor Engineering: Understanding the Role of Molecular Parameters for Thermoelectric Behaviors

Thermal activation energy for charge transfer (Eact,σ) plays a crucial role in determining the electrical properties of organic semiconductors, which are largely dominated by the Coulomb binding energy (Ecoul,ICTC) or static energy disorder (σICTC) of the formed integer charge transfer complexes at low or high doping concentration, respectively. Herein, we provide two typical donor-acceptor type polymers with distinct donors to disclose the role of molecular parameters in response for their corresponding thermoelectric (TE) behaviors. Noticeably, both the Ecoul,ICTC and σICTC of the polymers can be effectively restrained by varying the initial carbazole (CZ) donor to the dithieno[3,2-b:2',3'-d]pyrrole (DTP) moiety, which contributes to the remarkably decreased Eact,σ values of the PDTP-DPP than that of PCZ-DPP. Accordingly, the optimized power factors (PF) for PDTP-DPP (10.8 μW m-1 K-2) is almost 5 times higher than the primary PCZ-DPP (1.8 μW m-1 K-2) at ambient condition. In addition, a further improved PF over 85.5 μW m-1 K-2 can be achieved by PDTP-DPP at 488 K due to the synergy of thermal-induced dedoping and thermal-activated semiconducting behavior. Ultraviolet photoelectron and X-ray photoelectron spectroscopy measurements confirm the lower thermal activation energy for efficient p-doping of PDTP-DPP than that of PCZ-DPP.

Temperature Dependence of the Energy Transfer in LHCII Studied by Two-Dimensional Electronic Spectroscopy.

We measured two-dimensional electronic spectra of light-harvesting complex II (LHCII) at various temperatures (77, 110, 150, 230, and 295 K) under conditions free from singlet-singlet annihilation. We elucidated the temperature-dependent excitation energy transfer dynamics in the Chl a manifold of LHCII. Global analysis revealed that the dynamics can be summarized in distinct time scales from 200 fs up to 15 ps. While the fastest dynamics with a decay time of ∼0.2-0.3 ps are relatively temperature-independent, the lifetimes and relative contributions of slower components showed considerable temperature dependence. The slowest time scale of equilibration with the lowest-energy Chl a increased from ∼5 ps at 295 K to ∼15 ps at 77 K. The final excited state is independent of initial excitation at 230 K and above, whereas static energy disorder is apparent at lower temperatures. A clear temperature dependence of uphill energy transfer processes was also discerned, which is consistent with the detailed-balance condition.

High-pressure control of photosynthetic excitons

In photosynthesis, collective pigment excitations – excitons – facilitate chemical reactions for sustainable biological function. Here, the effect of hydrostatic pressure – an important thermodynamic stress factor – on optical spectral properties of excitons in the cyclic light-harvesting 2 pigment-protein complex from photosynthetic bacterium Rhodoblastus acidophilus was first studied. The high pressure-induced modifications of absorption, fluorescence and polarized fluorescence excitation spectra were theoretically analyzed in terms of the disordered molecular exciton model. We uniquely show that the observed shift of the spectra under pressure is largely governed by the pressure-induced rise of two factors: the exciton displacement energy and the exciton coupling energy, which increases the spread of the exciton state manifold. A significant increase of static energy disorder revealed by model calculations suggests that high-pressure compressing of the complex is actually accompanied by altered spatial orientations and conformations of the protein-embedded pigment molecules.

Origin of non-Gaussian site energy disorder in molecular aggregates

Gaussian site energy disorder is an ad hoc concept usually implemented in simulations of excitation dynamics in molecular systems. In this letter we suggest a mechanism which may cause correlated static energy disorder in a broad range of molecular systems. Our approach leads to non-Gaussian site energy distribution, which strongly affects statistical properties of exciton wavefunctions and consequently changes material functional characteristics.

Disorder-Induced Quantum Beats in Two-Dimensional Spectra of Excitonically Coupled Molecules.

Quantum superposition of molecular electronic states is very fragile because of thermal energy fluctuations and the static conformational disorder induced by the intimate surrounding of constituent molecules of the system. However, the nature of the long-lived quantum beats, observed in time-resolved spectra of molecular aggregates at physiological conditions, is still being debated. We present our study of the conditions when long-lived electronic quantum coherences originating from recently proposed inhomogeneous broadening mechanism are enhanced and reflected in the two-dimensional electronic spectra of the excitonically coupled molecular dimer. We show that depending on the amount of inhomogeneous broadening, the excitonically coupled molecular system can establish long-lived electronic coherences, caused by a disordered subensemble, for which the dephasing due to static energy disorder becomes significantly reduced. On the basis of these considerations, we present explanations for why the electronic or vibrational coherences were or were not observed in a range of recent experiments.

Symmetry-Based Analysis of the Effects of Random Energy Disorder on the Excitonic Level Structure of Cyclic Arrays: Application to Photosynthetic Antenna Complexes

We extend the work of Wu and Small who introduced symmetry-adapted basis defect patterns (BDPs) for systematic analysis of the effects of random static energy disorder (diagonal or off-diagonal) on the excitonic level structure of cyclic Cn arrays of chromophores. Examples include the B850 and B875 rings of bacteriochlorophyll (BChl) molecules associated with the LH2 and LH1 antenna complexes of purple bacteria for which, so far, n = 8, 9, and 16. Calculation of the localization/extendedness (chromophore occupation number) patterns and participation numbers of the exciton levels reveals that the effects of random disorder on the exciton levels that contribute to the critically important B850 or B875 absorption band can be understood in terms of a single BDP of e1 symmetry (“hidden correlation” effect). This is a consequence of the structures of the complexes, the complexes falling in the weak disorder regime and the strict symmetry selection rules that govern the couplings between zero-order exciton levels by BDPs. The above finding greatly simplifies computational studies on the effects of random disorder on the spectroscopic properties of the above bands. Our results show that interpretation of electric field (Stark) effects on the B850 and B875 absorption bands must include the effects of energy disorder. Similarities and differences between the effects of diagonal and off-diagonal energy disorder are discussed as is the relevance of our findings to the superradiant properties of the LH complexes.

Time Resolved Energy Migration in an Energetically Disordered Molecular Crystalt

Abstract Time resolved emission spectroscopy is used to monitor triplet exciton migration in p-dichloro-benzene-p-dibromobenzene mixed crystals. The migration efficiency is varied by adjusting the concentration and the temperature (2–12°K). Long range migration is found even though the static energy disorder parameter W is much larger than the exciton band width B. Because of exciton tunneling, the range of the transfer is only limited by the maximum lifetime of an exciton. These results illustrate the importance of at least six key parameters in determining the efficiency of long range exciton migration; B, W, the range of transfer, the temperature, the exciton lifetime and the topology of the excitation exchange interactions through its effect on the long range connectedness of the system.