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For conjugated macrocycles, conformational disorder plays a key role in determining whether the unique form of excitons that are fully delocalized over the cyclic framework (cyclic excitons) is formed by photoexcitation. We have investigated the ring size dependence of conformations and photophysical properties of macrocyclic thiophenes of varying ring sizes (C-5NTNV) by using single-molecule fluorescence spectroscopy. We measured modulation depth, M, values and fluorescence intensities. As the ring size increases, the correlation plots of the two parameters show bimodal distributions, revealing that larger macrocycles exhibit extremely congested linear structures. The size dependence of structural changes in macrocyclic thiophenes have been clearly confirmed by molecular dynamics simulation. The number of torsional defects from simulated structures, in conjunction with survival times from fluorescence intensity trajectories and photon coincidence measurements, demonstrated the existence of multiple acycl...

Density-corrected DFT is a method that cures several failures of self-consistent semilocal DFT calculations by using a more accurate density instead. A novel procedure employs the Hartree-Fock density to bonds that are more severely stretched than ever before. This substantially increases the range of accurate potential energy surfaces obtainable from semilocal DFT for many heteronuclear molecules. We show that this works for both neutral and charged molecules. We explain why and explore more difficult cases, for example, CH(+), where density-corrected DFT results are even better than sophisticated methods like CCSD. We give a simple criterion for when DC-DFT should be more accurate than self-consistent DFT that can be applied for most cases.

Linkers adjoining chromophores play an important role in modulating the structure of conjugated systems, which is bound up with their photophysical properties. However, to date, the focus of works dealing with linker effects was limited only to linear π-conjugated materials, and there have been no detailed studies on cyclic counterparts. Herein we report the linker effects on the dynamic planarization processes of π-conjugated macrocyclic oligothiophene 12-mers, where the different ratio between ethynylene and vinylene linkers was chosen to control the backbone rigidity. By analyzing transient fluorescence spectra, we demonstrate that the connecting linkers play a crucial role in the excited-state dynamics of cyclic conjugated systems. Faster dynamic planarization, longer exciton delocalization length, and higher degree of planarity were observed in vinylene inserted cyclic oligothiophenes. Molecular dynamics simulations and density functional theory calculations also stress the importance of the role of linkers in modulating the structure of cyclic oligothiophenes.

On the basis of a tight binding system-bath model, we investigated carrier mobility of PbSe nanocrystal (NC) arrays as a function of NC size and inter-NC separation. The size-dependent trend of calculated carrier mobilities are in excellent agreement with recent experimental measurements: electron mobility increased up to NC diameter of ∼6 nm and then decreased for larger NCs, whereas hole mobility showed a monotonic size-dependency. Carrier mobility increase was associated with reduced activation energy that governs charge-transfer processes. In contrast, the decrease in electron mobility for large NCs was found to be due to smaller electronic coupling. Control of inter-NC separation is crucial for mobility enhancement: the mobility may change by an order of magnitude when inter-NC separation varies by as little as 1 to 2 A. We anticipate similar size-dependency of the mobility in other semiconductor NC arrays, although crossover diameter in which mobility reaches its maximum depends on the material.