π-Conjugated molecule-bridged silicon quantum dot (Si QD) clusters were first synthesized by Sonogashira cross-coupling reaction between 4-ethynylstyryl and octyl co-capped Si QDs (4-Es/Oct Si QDs) and 2,5-dibromo-3-hexylthiophene. The formation of Si QD clusters was confirmed by field emission transmission electron microscopy. The electronic coupling between the QDs in the Si QD cluster is significantly enhanced as compared with that for 4-Es/Oct Si QDs, which is verified from the red shift in ultraviolet–visible absorption and photoluminescence spectra of the Si QD cluster with the possibility of exciton transport, the increased charging effect found in the core-level photoemission spectra, the shift to lower binding energy of the valence band photoemission spectrum, and more decisively, the increase in electrical conductance of the Si QD cluster thin film. To investigate the physical origin of the temperature dependence of the electrical conductance, we have merged the microscopic viewpoint, Marcus theory, on the electron transfer ( W ) between the adjacent QDs, with macroscopic concepts, such as the conductance ( G ), mobility (μ), and diffusion coefficient ( D ). The effective reorganizational energies of charge transfer between the neighboring Si QDs in 4-Es/Oct Si QD and Si QD cluster thin films are estimated to be 170 and 140 meV, respectively, while the ratio of the effective electronic coupling of the latter to that of the former is determined to be 7.3:1.

π-Conjugated molecule bridged silicon quantum dots (Si QDs) cluster was prepared by Sonogashira C−C cross-coupling reaction between 4-bromostyryl and octyl co-capped Si QDs (4-Bs/Oct Si QDs) and 1,4-diethynylbenzene. The surface chemical structure, morphology, and chemical composition of the Si QD cluster were confirmed by Fourier transform infrared spectroscopy, field emission transmission electron microscopy, and energy-dispersive X-ray spectroscopy. Lithiumion batteries were fabricated using 4-Bs/Oct Si QD and Si QD clusters as anode materials to investigate the effect of QD clustering on the electrochemical performance. Compared with the 4-Bs/Oct Si QD electrode, the Si QD cluster exhibits improved electrochemical performance, such as a high initial discharge capacity of ∼1957 mAh/g and good cycling stability with ∼63% capacity retention following 100 cycles at a current rate of 200 mA/g when tested at the voltage window of 0.01−2.5 V. The improved electrochemical performance of the Si QD cluster is attributed to the π-conjugated molecules between the Si QDs and on the surface of Si QD cluster, which serve as a buffer layer to alleviate the mechanical stresses arising from the alloying reaction of Si with lithium and maintain the electrical conduits in the anode system.

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We developed a MATLAB algorithm to calculate reorganization energy utilizing rectilinear normal mode displacements. Normal mode‐projected rectilinear displacements and the corresponding angular frequencies, required for evaluating charge transfer reorganization energy within the harmonic oscillator approximation, were obtained from Cartesian coordinates and Cartesian force constant matrices determined with respect to the principal axes. To verify the algorithm developed with MATLAB, we compared the computed charge transfer reorganization energies to those evaluated by the DUSHIN program, and there was no substantial difference, indicating that our algorithm guarantees the numerical accuracy of the calculations. This algorithm was applied to design silicon quantum dots (Si QDs) with low reorganization energies for charge transfer.

To assess the influence of bridge structure manipulation on the electrochemical performance of π-conjugated molecule-bridged silicon quantum dot (Si QD) nanocomposite (SQNC) anode materials, we prepared two types of SQNCs...