Angelica Lundin

Comparative Ab-Initio Study of Substituted Norbornadiene- Quadricyclane Compounds for Solar Thermal Storage

Molecular photoswitches that are capable of storing solar energy, so-called molecular solar thermal storage systems, are interesting candidates for future renewable energy applications. In this context, substituted norbornadiene-quadricyclane systems have received renewed interest due to recent advances in their synthesis. The optical, thermodynamic, and kinetic properties of these systems can vary dramatically depending on the chosen substituents. The molecular design of optimal compounds therefore requires a detailed understanding of the effect of individual substituents as well as their interplay. Here, we model absorption spectra, potential energy storage, and thermal barriers for back-conversion of several substituted systems using both single-reference (density functional theory using PBE, B3LYP, CAM-B3LYP, M06, M06-2x, and M06-L functionals as well as MP2 calculations) and multireference methods (complete active space techniques). Already the diaryl substituted compound displays a strong red-shift compared to the unsubstituted system, which is shown to result from the extension of the conjugated π-system upon substitution. Using specific donor/acceptor groups gives rise to a further albeit relatively smaller red-shift. The calculated storage energy is found to be rather insensitive to the specific substituents, although solvent effects are likely to be important and require further study. The barrier for thermal back-conversion exhibits strong multireference character and as a result is noticeably correlated with the red-shift. Two possible reaction paths for the thermal back-conversion of diaryl substituted quadricyclane are identified and it is shown that among the compounds considered the path via the acceptor side is systematically favored. Finally, the present study establishes the basis for high-throughput screening of norbornadiene-quadricyclane compounds as it provides guidelines for the level of accuracy that can be expected for key properties from several different techniques.

Quantum chemical modeling of propene and butene epoxidation with hydrogen peroxide.

The mechanism of hydrogen peroxide assisted epoxidation of propene, 1-butene, trans-2-butene, cis-2-butene, and isobutene was studied using density functional theory calculations. The results are rationalized in the context of the previously proposed direct pathway for epoxidation of ethene with hydrogen peroxide and compared to the indirect pathway involving Ti(IV) peroxide groups. The indirect Ti(IV) peroxide pathway displays a 57.8 kJ mol(-1) activation enthalpy for the rate limiting step [Phys. Chem. Chem. Phys. 2007, 9, 5997]. In contrast, a lowering of the activation enthalpy is observed for the direct mechanism according to 72.3 (ethene), 53.9 (1-butene), 53.5 (propene), 46.9 (trans-2-butene), 46.6 (isobutene), and 42.6 (cis-2-butene) kJ mol(-1) when the reaction takes place on a binuclear Ti(IV) dihydroxide site. These values clearly show that the direct pathway becomes the most favorable. The stability of the epoxides toward hydrolysis to the corresponding diols are also addressed. The present work clearly demonstrates the generality and efficiency of a binuclear dihydroxide site in catalyzing the epoxidation of olefins with hydrogen peroxide, thus avoiding the formation of a surface peroxide group.

Computational modelling of donor–acceptor conjugated polymers through engineered backbone manipulations based on a thiophene–quinoxaline alternating copolymer

The rapid progress of bulk heterojunction organic photovoltaics has been boosted by (i) design and synthesis of novel conjugated donor materials, (ii) control and optimization of device fabrication, and (iii) the development of new device architectures such as tandem and ternary solar cells. Computationally driven material design has attracted increasing interest to accelerate the search for optimal conjugated photovoltaic materials, and the exploration of chemical methodologies is highly desirable in pushing the efficiency further towards the theoretical limit. Based on the motif of donor–acceptor polymers, around 50 comparable polymers were constructed and investigated, derived from an easily accessible thiophene–quinoxaline alternating polymer donor showing power conversion efficiency up to 7%. We performed a systematic density functional theory (DFT) study on the heteroatom effects of combining fluorine, nitrogen and chalcogen substitutions onto the donor/acceptor units as well as the effect of extending π-conjugation in the donor moiety, in order to gain insight into how structural modifications to the conjugated backbone can affect the molecular structure and electronic properties of a conjugated polymer. It is found that the trends in the energy levels and band gaps of these polymers correlate well with their structural modifications. Finally, by examining the systematically evaluated data in the energy diagram, we proposed three important ways of energy level modulation, showing potential chemical methodologies that can be applicable to further modify and optimize existing polymer backbones. Especially such energy level modulation can be applied to meet the particular requirements of different device architectures (including tandem and ternary solar cells) on the donor components, such as a prominent photocurrent or photovoltage combined with a high efficiency, to further maximize the overall performance of organic photovoltaics. This will provide valuable guidance and chemical methodologies for a judicious material design of conjugated polymers for solar cell applications with desirable photovoltaic characteristics.

Optimization of Norbornadiene Compounds for Solar Thermal Storage by First‐Principles Calculations

Molecular photoswitches capable of storing solar energy are interesting candidates for future renewable energy applications. Here, using quantum mechanical calculations, we carry out a systematic screening of crucial optical (solar spectrum match) and thermal (storage energy density) properties of 64 such compounds based on the norbornadiene-quadricyclane system. Whereas a substantial number of these molecules reach the theoretical maximum solar power conversion efficiency, this requires a strong red-shift of the absorption spectrum, which causes undesirable absorption by the photoisomer as well as reduced thermal stability. These compounds typically also have a large molecular mass, leading to low storage densities. By contrast, single-substituted systems achieve a good compromise between efficiency and storage density, while avoiding competing absorption by the photo-isomer. This establishes guiding principles for the future development of molecular solar thermal storage systems.

High electron affinity: a guiding criterion for voltage stabilizer design

Voltage stabilizers are an emerging class of additives that enhance the dielectric strength of an insulating polymer such as polyethylene. Several partially conflicting reports ascribe the stabilizing effect to either a high electron affinity or low ionization potential of the additive. Here, we report a clear correlation of the electron affinity and to a lesser extent the EHOMO–ELUMO difference of various voltage stabilizers with electrical tree initiation in cross-linked polyethylene. To facilitate a fair evaluation, the voltage-stabilizing efficiency of a set of 13 previously reported voltage stabilizers, which strongly differ in their chemical composition, is compared at equal stabilizer concentration and equivalent test methodology. These results are correlated with the electron affinity and EHOMO–ELUMO difference, as obtained from density functional theory (DFT) modeling, which agreed well with available literature values. Moreover, based on the here established strong correlation between dielectric strength and electron affinity, a new molecule with exceptionally high electron affinity is selected from the extended literature on organic photovoltaics. This malononitrile–benzothiadiazole–triarylamine based molecule with a high electron affinity of 3.4 eV gives rise to a 148% increase in tree initiation field compared to 40% obtained using anthracene, one of the most efficient previously reported voltage-stabilizers, under equivalent test conditions. Thus, we here propose to use the electron affinity as a guiding criterion for identifying novel high-efficiency voltage stabilizers, which opens up the vast library of organic semiconductors as potential candidates, as well as associated synthesis routines for the design of yet unexplored materials.

The Influence of Alkoxy Substitutions on the Properties of Diketopyrrolopyrrole-Phenyl Copolymers for Solar Cells

A previously reported diketopyrrolopyrrole (DPP)-phenyl copolymer is modified by adding methoxy or octyloxy side chains on the phenyl spacer. The influence of these alkoxy substitutions on the physical, opto-electronic properties, and photovoltaic performance were investigated. It was found that the altered physical properties correlated with an increase in chain flexibility. Well-defined oligomers were synthesized to verify the observed structure-property relationship. Surprisingly, methoxy substitution on the benzene spacer resulted in higher melting and crystallization temperatures in the synthesized oligomers. This trend is not observed in the polymers, where the improved interactions are most likely counteracted by the larger conformational possibilities in the polymer chain upon alkoxy substitution. The best photovoltaic performance was obtained for the parent polymer: fullerene blends whereas the modifications on the other two polymers result in reduced open-circuit voltage and varying current densities under similar processing conditions. The current densities could be related to different polymer: fullerene blend morphologies. These results show that supposed small structural alterations such as methoxy substitution already significantly altered the physical properties of the parent polymer and also that oligomers and polymers respond divergent to structural alterations made on a parent structure.

Tuning the photochemical properties of the fulvalene-tetracarbonyl-diruthenium system

In a Molecular Solar-Thermal Energy Storage (MOST) system, solar energy is converted to chemical energy using a compound that undergoes reversible endothermic photoisomerization. The high-energy photoisomer can later be converted back to the parent compound and the excess energy is released as heat. One of the most studied MOST systems is based on fulvalene-tetracarbonyl-diruthenium, and this paper demonstrates, for the first time, the possibility to tune the photochemical properties of this system by positive steric hindrance working on the fulvalene unit.