Spontaneous polarization of a nonpolar molecule upon photoexcitation (the sudden polarization effect) earlier discussed for 90°-twisted alkenes is observed and calculated for planar ring-fluorinated stilbenes, trans-2,3,5,6,2',3',5',6'-octofluorostilbene (tF2356) and trans-2,3,4,5,6,2',3',4',5',6'-decafluorostilbene (tF23456). Due to the fluorination, Franck-Condon states S and S are dominated by the quasi-degenerate HOMO-1 → LUMO and HOMO-2 → LUMO excitations, while their interaction gives rise to a symmetry-broken zwitterionic S state. After optical excitation of tF2356, one observes an ultrafast (∼0.06 ps) evolution that reflects relaxation from initial nonpolar S to long-lived (1.3 ns in n-hexane and 3.4 ns in acetonitrile) polar S. The polarity of S is evidenced by a solvatochromic shift of its fluorescence band. The experimental results provide a sensitive test for quantum-chemical calculations. In particular, our calculations agree with the experiment, and raise concerns about the applicability of the common TDDFT approach to relatively simple stilbenic systems.
We investigate THz radiation absorption by charge carriers, focusing on the mobility in nanorods and wires. We show that for short rods the mobility is limited by the high spacing...
Herein, the THz mobility of charge carriers in low‐dimensional semiconductors based on a density matrix approach involving master equations for population and polarization dynamics is modeled. Pulsed THz fields induce intraband transitions between quantized subband states, creating polarization and subsequent charge transport that governs the electron mobility. It is shown that an equilibration current emerges—a purely quantum mechanical contribution understood via the Ehrenfest theorem in 1D—reshaping the low‐frequency mobility. Apart from thermal population, the results further demonstrate that the frequency‐dependent mobility becomes THz field strength and spectrum, as well as pulse width and chirp dependent, already at moderate THz probe fields of 1 kV cm−1, e.g., for 1D CdSe or GaAs nanostructures. The parametric nature of the underlying master differential equations for polarization and population, driving the intraband conductivity, results in a nonlinear, third‐order mobility and susceptibility, causing a nontrivial field dependence as well as power broadening even at moderate field strength. The obtained results are in good agreement with experiments. The observed high nonlinearities strongly impact the design and interpretation of THz charge carrier mobility experiments and further allow applications like coherent control, frequency mixing, or synthesis through a field‐controlled nonlinearity or high harmonics generation, especially interesting for future 6G telecommunication.
Although seminaphtorhodafluor (SNARF) dyes are already widely used to measure pH in cells and at biofilms, their synthesis has low yield and results in an unspecific position of a carboxy-group. The separation of 5'- and 6'-carboxy-SNARF reveals a pKa difference of 0.15, calling into question pH measurements with the (commercially available) mixture. Here we replace the bulky external dicarboxyphenyl ring with a propionate group and evaluate the spectral properties of the new derivative. Proceeding to the ethyl-iodoacetamide, covalent linkage to cysteine protein sites is achieved efficiently as shown with a cyanobacterial phytochrome, extending the scarce application of SNARF in bio-labelling in the current literature. Application in fluorescence lifetime imaging is demonstrated both with the lifetime-based and ratiometric-yield method.
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