Organic semiconductors are inherently soft,making it possible to increase their mobilities by strains.Such a unique feature can be exploited directly in flexible electronics for improved device performance.The 2,7-dioctyl[1]benzothieno[3,2-b][1]-benzothiophene derivative,C8-BTBT is one of the best small-molecule hole transport materials.Here,we demonstrated its band structure modulation under strains by combining the non-equilibrium molecular dynamics simulations and first-principles calculations.We found that the C8-BTBT lattice undergoes a transition from monoclinic to triclinic crystal system at the temperature below 160 K.Both shear and uniaxial strains were applied to the low-temperature triclinic phase of C8-BTBT,and polymorphism was identified in the shear process.The band width enhancement is up to 8%under 2%of compressive strain along the x direction,and 14%under 4%of tensile strain along the y direction.The band structure modulation of C8-BTBT can be well related to its herringbone packing motifs,where the edge to face and edge to edge pairs constitute two-dimensional charge transport pathways and their electronic overlaps determine the band widths along the two directions respectively.These findings pave the way for utilizing strains towards improved performance of organic semiconductors on flexible substrates,for example,by bending the substrates.
We present here a brief summary of a National Natural Science Foundation Major Project entitled "Theoretical study of the low-lying electronic excited state for molecular aggregates". The project focuses on theoretical investigation of the electronic structures and dynamic processes upon photo-and electric-excitation for molecules and aggregates. We aim to develop reliable methodology to predict the optoelectronic properties of molecular materials related to the electronic excitations and to apply in the experiments. We identify two essential scientific challenges: (i) nature of intramolecular and intermolecular electronic excited states; (ii) theoretical description of the dynamic processes of the coupled motion of electronic excitations and nucleus. We propose the following four subjects of research: (i) linear scaling time-dependent density-functional theory and its application to open shell system; (ii) computational method development of electronic excited state for molecular aggregates; (iii) theoretical investigation of the time evolution of the excited state dynamics; (iv) methods to predict the optoelectronic properties starting from electronic excited state investigation for organic materials and experimental verifications.
In this work, the intra-EDA method, which is a recently developed energy decomposition analysis scheme for intramolecular non-covalent interaction is extended from gas phase to solvated environment. It is the first analysis scheme that performs analysis for intramolecular interaction in solution. By fragmentation scheme, a molecule is divided into intramolecular interacting fragments and environmental fragments via single bond homolysis breaking. The solvent effect is taken into account by implicit solvation model. Intramolecular interaction free energy is estimated as the separated treatment of inter-fragment interactions in dielectric environment. The analysis results highlight the importance of solvent effects to intramolecular non-covalent interaction.
