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Dynamic disorder manifested in fluctuations of charge transfer integrals considerably hinders charge transport in high-mobility organic semiconductors. Accordingly, strategies for suppression of the dynamic disorder are highly desirable. In this study, we suggest a novel promising strategy for suppression of dynamic disorder-tuning the molecular electrostatic potential. Specifically, we show that the intensities of the low-frequency (LF) Raman spectra for crystalline organic semiconductors consisting of π-isoelectronic small molecules (i.e. bearing the same number of π electrons)-benzothieno[3,2-b][1]benzothiophene (BTBT), chrysene, tetrathienoacene (TTA) and naphtho[1,2-b:5,6-b']dithiophene (NDT)-differ significantly, indicating significant differences in the dynamic disorder. This difference is explained by suppression of the dynamic disorder in chrysene and NDT because of stronger intermolecular electrostatic interactions. As a result, guidelines for the increase of the crystal rigidity for the rational design of high-mobility organic semiconductors are suggested.

One of the major challenges in the field of organic photovoltaics is associated with high-throughput manufacturing of efficient and stable organic solar cells. Practical realization of technologies for production of large-area organic solar cells requires the development of novel materials with a defined combination of properties ensuring sufficient reliability and scalability of the process in addition to good efficiency and operation stability of the devices. In this work, we designed two novel polymers comprising thiazolothiazole units and investigated their performance as absorber materials for organic solar cells and modules. Optimized small-area solar cells based on P1/[70]PCBM ([6,6]-phenyl-C71-butyric acid methyl ester) blends exhibited promising power conversion efficiency (PCE) of 7.5%, while larger area modules fabricated using slot die coating showed encouraging PCE of 4.2%. Additionally, the fabricated devices showed promising outdoor stability maintaining 60–70% of the initial efficiency after 20 sun days being exposed to natural sunlight at the Negev desert. The obtained results feature the designed polymer P1 as a promising absorber material for a large-scale production of organic solar cells under ambient conditions.

Phenomena ranging from vitrification to crystal nucleation are governed by locally ordered structures, in otherwise disordered phases, that can either inhibit or favour the growth of macroscopic order. However, such structures are ephemeral, do not typically have distinct spectral features, and are therefore critically important but largely unobservable by current methods. Illuminating these structures therefore presents the single greatest challenge in physical chemistry. The boson peak is characteristic of glasses and represents the locally ordered structures inhibiting crystallisation but is typically obscured by other spectral contributions. Here we show that depolarised Raman scattering—obtained using femtosecond optical Kerr-effect spectroscopy—in liquids consisting of highly symmetric molecules can be used to isolate the boson peak thereby allowing detailed characterisation of the intermolecular potential-energy landscape for the first time.

Equilibrium geometry parameters, harmonic vibrational frequencies and barriers to conformational transitions and conformer energy differences for N-methylacetamide (CH3CONHCH3) molecule in S0, S1 and T1 electronic states were calculated in MP2 (S0) and CASPT2 (S1, T1) levels of theory. It is known that there are two planar (or effectively planar) conformers of N-methylacetamide in the ground electronic state. It is proved that the electronic excitation to aforementioned electronic states resulted in both CCON and HNCC fragments becoming pyramidal and rotated around «central» CN bond. One-, two- and three-dimensional potential energy surface (PES) sections by different large amplitude motions (LAM) coordinates were obtained by MP2 (S0) and CASPT2 (S1, T1) methods with cc-pVTZ basis set. On 2D PES sections by «central» torsion (CN) and one of the CCON or HNCC fragments’ inversion coordinates there are six different minima. Using PES sections as the potentials in model Hamiltonians, different anharmonic vibrational problems were solved and the frequencies of large amplitude vibrations were estimated variationally.

Conformational space of polyphenylenevinylene oligomers is systematically investigated computationally at energies relevant for room temperature dynamics in a solvent and in a solid state. Our calculations show that optimal oligomer structures are essentially planar. However, lack of a deep minimum at the planar geometry allows for large molecular deformations even at very low temperatures. At larger angles, rotational motion of dihedrals intermix with two orthogonal bending motions of the entire molecule. In a crystalline environment these degrees of freedom intermix with translational and rotational motions, whereas purely intramolecular modes are well separated. The reliability of our calculations is confirmed by an excellent match of the theoretical and experimental Raman spectra of crystalline stilbene in the entire spectral range including the low-frequency part. Obtained results provide important insights into nature of low-frequency vibrations, which play a key role in charge transport in organic semiconductors.

For conformers of the N -methylformamide (HCONHCH 3 ) molecule, calculations of equilibrium geometry parameters, harmonic vibration frequencies, energy differences and potential barriers to conformational transitions were performed in the ground (S 0 ) and lowest excited singlet (S 1 ) and triplet (T 1 ) electronic states. In the S 0 state, the molecule exists in trans and cis stable conformations (having C s symmetry). Our calculations show that the electronic excitations T 1 ←S 0 and S 1 ←S 0 cause changes in the structure of conformers: both HCON and HNCC fragments become pyramidal and rotate around the CN bond. As a result, in each excited electronic state under consideration, there are 12 minima forming six pairs of equivalent conformers separated by relatively small potential barriers. One- and two-dimensional potential energy surface sections corresponding to different intramolecular large-amplitude motions were calculated using the MP2/aug-cc-pVTZ (S 0 ) and CASPT2/cc-pVTZ (S 1 and T 1 ) methods. Anharmonic vibrational problems for large-amplitude motions were solved, and the corresponding frequencies were estimated.

A series of ten conjugated polymers incorporating in their molecular frameworks extended DADAD building blocks with thiophene donor (D) and either benzotriazole, benzoxadiazole, benzothiadiazole, difluorobenzothiadiazole or quinoxaline acceptor (A) units were synthesized and characterized. The optoelectronic properties of new polymers were computed and experimentally investigated revealing a good relationship, which can guide further rational design of materials with tailored properties for organic photovoltaics using in-silico approaches. The performance of all polymers in organic bulk heterojunction solar cells was compared and some important empirical rules were formulated for reaching the best photovoltaic performance from (X-DADAD)n family of polymers.

Electron-phonon interaction strongly affects and often limits charge transport in organic semiconductors (OSs). However, approaches to its experimental probing are still in their infancy. In this study, we probe the local electron-phonon interaction (quantified by the charge-transfer reorganization energy) in small-molecule OSs by means of Raman spectroscopy. Applying density functional theory calculations to four series of oligomeric OSs-polyenes, oligofurans, oligoacenes, and heteroacenes-we extend the previous evidence that the intense Raman vibrational modes considerably contribute to the reorganization energy in several molecules and molecular charge-transfer complexes, to a broader scope of OSs. The correlation between the contribution of the vibrational mode to the reorganization energy and its Raman intensity is especially prominent for the resonance conditions. The experimental Raman spectra obtained with various excitation wavelengths are in good agreement with the theoretical ones, indicating the reliability of our calculations. We also establish for the first time relations between the spectrally integrated Raman intensity, the reorganization energy, and the molecular polarizability for the resonance and off-resonance conditions. The results obtained are expected to facilitate the experimental studies of the electron-phonon interaction in OSs for an improved understanding of charge transport in these materials.

Four new conjugated polymers based on benzodithiophene, thiophene and 2,1,3-benzothiadiazole or 5,6-difluoro-2,1,3-benzothiadiazole were synthesized and investigated as absorber materials for organic photovoltaics. The effect of (bi)thiophene π-spacers and fluorine substitution on the physicochemical and optoelectronic properties of the polymers was revealed and correlations were drawn with their electrical characteristics in organic solar cells. In particular, introducing either thiophene spacers or fluorine substituents does not affect much the photovoltaic performance of the polymers, while the combination of both routes was found to be a promising strategy for improving the charge carrier mobilities and morphology of the polymer-fullerene blends as well as light power conversion efficiency in solar cells based on these materials. The bulk heterojunction organic solar cells based on the π-bridged and fluorinated polymer P4 showed the highest short-circuit current density and power conversion efficiency of 7 %, which is an inspiring value for fullerene-based organic photovoltaics. Most importantly, our findings provide important insights into rational design of high-performance conjugated polymers while pursuing a combination of two efficient backbone functionalization strategies based on introduction of fluorine substituents and π-spacers to control the geometry and electronic characteristics of the polymer chains.

For the formamide, acetamide, N-methylformamide and N-methylacetamide molecules in the ground (S0 ) and lowest excited singlet (S1 ) and triplet (T1 ) electronic states equilibrium geometry parameters, harmonic vibrational frequencies, barriers to conformational transitions and conformer energy differences were estimated by means of MP2, CCSD(T), CASSCF, CASPT2 and MRCI ab initio methods. One-, two- and three-dimensional potential energy surface (PES) sections corresponding to different large amplitude motions (LAM) were calculated by means of MP2/aug-cc-pVTZ (S0 ) and CASPT2/cc-pVTZ (S1 ,T1 ). For these molecules, in each excited electronic state six minima were found on 2D PES sections. Using PES sections, different anharmonic vibrational problems were solved and the frequencies of large amplitude vibrations were determined.

Low-frequency vibrations play an essential role in biomolecular processes involving DNA such as gene expression, charge transfer, drug intercalation, and DNA–protein recognition. However, understanding the vibrational basis of these mechanisms relies on theoretical models due to the lack of experimental evidence. Here we present the low-frequency vibrational spectra of G-quadruplexes (structures formed by four strands of DNA) and B-DNA characterized using femtosecond optical Kerr-effect spectroscopy. Contrary to expectation, we found that G-quadruplexes show several strongly underdamped delocalized phonon-like modes that have the potential to contribute to the biology of the DNA at the atomic level. In addition, G-quadruplexes present modes at a higher frequency than B-DNA demonstrating that changes in the stiffness of the molecule alter its gigahertz to terahertz vibrational profile., Low-frequency vibrations play an essential role in biomolecular processes involving DNA such as gene expression, charge transfer, drug intercalation, and DNA–protein recognition.