Ferrocene Molecular Architectures Grafted on Si(111): A Theoretical Calculation of the Standard Oxidation Potentials and Electron Transfer Rate Constant

The standard oxidation potential and the electron transfer (ET) rate constants of two silicon-based hybrid interfaces, Si(111)/organic-spacer/Ferrocene, are theoretically calculated and assessed. The dynamics of the electrochemical driven ET process is modeled in terms of the classical donor/acceptor scheme within the framework of Marcus theory. The ET rate constants, k(ET), are determined following calculation of the electron transfer matrix element, V-RP, together with the knowledge of the energy of the neutral and charge separated systems. The recently introduced Constrained Density Functional Theory (CDFT) method is exploited to optimize the structure and determine the energy of the charge separated species. Calculated ET rate constants are k(ET) = 77.8s(-1) and k(ET) = 1.3 x 10(-9) s(-1), in the case of the short and long organic-spacer, respectively

An Integrated Experimental/Theoretical Study of Structurally Related Poly-Thiophenes Used in Photovoltaic Systems

In this work, a series of eight thiophene-based polymers (exploited as “donors” in bulk heterojunction photovoltaics cells), whose structures were designed to be suitably tuned with the electronic characteristics of the [6,6]-Phenyl C61 butyric acid methyl ester (PCBM), is considered,. The electronic properties of the mono-, di-, trimeric oligomers are reckoned (at the Hartree-Fock and DFT level of the theory) and compared to experimental spectroscopic and electrochemical results. Indeed, electrochemical and spectroscopic results show a systematic difference whose physical nature is assessed and related to the exciton (electron-hole) binding energy (Je,h). The critical comparison of the experimental and theoretical band gaps, i.e., the HOMO-LUMO energy difference, suggests that electrochemical and DFT values are the most suited to being used in the design of a polythiophene-based p-n junction for photovoltaics

Control of polymorphism in coronene by the application of magnetic fields

Coronene, a polyaromatic hydrocarbon, has been crystallized for the first time in a different polymorph using a crystal growth method that utilizes magnetic fields to access a unit cell configuration that was hitherto unknown. Crystals grown in magnetic field of 1 T are larger, have a different appearance to those grown in zero field and retain their structure in ambient conditions. We identify the new form, beta-coronene, as the most stable at low temperatures. As a result of the new supramolecular configuration we report significantly altered electronic, optical and mechanical properties.Comment: 32 pages, 17 figure

First-Principles Estimation of Core Level Shifts for Hf, Ta, W, and Re

A simple first-principles approach is used to estimate the core level shifts observed in X-ray photoelectron spectroscopy for the 4f electrons of Hf, Ta, W, and Re; these elements were selected because their 4f levels are relatively close to the Fermi energy. The approach is first tested by modeling the surface core level shifts of low-index surfaces of the four elemental metals, followed by its application to the well-studied material TaSe2 in the commensurate charge density wave (CDW) phase, where agreement with experimental data is found to be good, showing that this approach can yield insights into modifications of the CDW. Finally, unterminated surface core level shifts in the hypothetical MXene Ta3C2 are modeled, and the potential of XPS for the investigation of the surface termination of MXenes is demonstrated

Optical response of the bulk stabilized mosaic phase in Se doped TaS2−x_{2-x}Sex_{x}

The layered van der Waals material, TaS$_{2}$ features a meta-stable mosaic phase on the verge of a nearly commensurate to commensurate charge density wave transition. This meta-stable or 'hidden' phase can be reached by laser pumping the low temperature, commensurate charge density wave phase. Here we report the stabilization of a bulk, equilibrium mosaic phase in 1T-TaS$_{1.2}$Se$_{0.8}$ single crystals observed with transport and optical spectroscopy experiments. We identify a bulk pseudogap in the mosaic phase of approximately 200 meV at the lowest temperatures, while the CCDW phase can be obtained by heating and instead has a full optical gap of about 100 meV. Surprisingly, a spectral weight analysis shows that Se doping gives rise to an increased charge density despite the fact that this is formally an isovalent substitution. This finding is consistent with the recent observation that the mosaic phase is stabilized as equilibrium phase through the appearance of charged defects.Comment: 7 pages, 3 figure

Enhanced photogeneration of polaron pairs in neat semicrystalline donor-acceptor copolymer films via direct excitation of interchain aggregates

We investigate the photogeneration of polaron pairs (PPs) in neat films of the semicrystalline donor–acceptor semiconducting copolymer PCPDTBT. Carefully selecting the solution-processing procedures, we obtain films with different amounts of crystallinity and interchain aggregation. We compare the photogeneration of PPs between the films by monitoring their photoinduced absorption in ultrafast pump–probe experiments, selectively exciting nonaggregated or aggregated polymer chains. The direct photoexcitation of interchain π-aggregates results in prompt (<100 fs) charge generation. Compared to the case where nonaggregated chains are excited, we find an 8-fold increase in the prompt PP to singlet-exciton ratio. We also show that highly crystalline lamellar nanostructures not containing π-stacked or any light-absorbing aggregates do not improve the efficiency of PP photogeneration. Our results show that light absorption from interchain aggregates is highly beneficial for charge photogeneration in semiconducting polymers and should be taken into account when optimizing film morphologies for photovoltaic devices

Charge transfer modulation in charge transfer co-crystals driven by crystal structure morphology

The electronic properties of a charge-transfer (donor-acceptor) semiconducting organic co-crystal, Perylene:F4-TCNQ (PE:F4) (the donor, D, is PE and the acceptor, A, is 2,3,5,6-tetrafluoro-7,7,8,8 tetracyanoquinodimethane (F4)) in its 3 : 2 stoichiometry, are experimentally and theoretically studied. This is performed by means of electron paramagnetic resonance (EPR) and solid state electrochemical techniques, such as cyclic voltammetry (CV) measurements on single crystals. In particular, solid state electrochemistry proves to be an effective tool to probe, on a macroscopic scale, the electronic characteristics of the co-crystal. However, EPR highlights the presence of spin 1/2 radicals localized on F4 molecules, possibly linked to defects. The experimental findings are discussed on the basis of density functional theory (DFT) based calculations, carried out using both the projector augmented wave (PAW), with "periodic boundary conditions" (pbc), method and the localized orbitals, molecular cluster, approach. In particular, a satisfying agreement is found between the experimental, 0.336 eV (electrochemical), and theoretical, 0.303 eV (PAW), band gaps. Differences with the reported optical bandgap are discussed considering excitonic effects

Near infrared ultrafast pump-probe spectroscopy with ZrF4-BaF2-LaF3-AlF3-NaF fiber supercontinuum

We report on the performance of a setup designed for femtosecond pump-probe spectroscopy in the near infrared (NIR) spectral region. We generate a supercontinuum (SC) probe by coupling 140 fs light pulses at 1550 nm into a ZrF4-BaF2-LaF3-AlF3-NaF (ZBLAN) fiber. The combined high nonlinearity and transparency of the ZBLAN fluoride glass allows us to obtain a SC probe from 1 to 2.6 μm. The NIR pulses are used to demonstrate a proof of principle experiment probing the relaxation of photo induced excitations in a conjugated polymer:fullerene blend film. The results show the possibility to perform fibre based NIR SC femtosecond spectroscopy at &gt;100 KHz repetition rate and using lasers with pulse energy just above 300 nJ