Abstract:We have constructed an ultrahigh vacuum confocal fluorescence microscope with the purpose of performing single molecule spectroscopy under highly defined conditions. The microscope is designed for high stability while affording the capability of sample preparation, sample transfer, and optical detection in ultrahigh vacuum. It achieves near-diffraction-limited performance and allows the observation of single molecule fluorescence dynamics over extended periods of time. The design of the microscope is discussed… Show more
“…Under this assumption, the emission from a SM will conform to two intensities, one for emission from the optically prepared state and another when the molecule populates a nonemissive state. However, recent applications of sophisticated algorithms such as change-point detection (CPD) in the analysis of SM emission have shown that multiple intensity states are present. − Why would a SM demonstrate more than a single emission intensity? One explanation is spectral diffusion, environmental fluctuations of the ground-excited state energy gap altering the photoexcitation rate, and subsequently the emission intensity .…”
The connection between photoluminescence (PL) intermittency and excited-state kinetics is explored for 2',7'-dichlorofluorescein (DCF) isolated in crystals of potassium acid phthalate (KAP) using time-tagged, time-resolved, time-correlated single-photon counting (T3R-TCSPC). In this technique, PL intermittency or "blinking" is measured in conjunction with the time of photon arrival relative to photoexcitation, allowing for the correlation of emissive intensities and excited-state decay kinetics of single molecules. The blinking trace is parsed into emissive and nonemissive segments using change-point-detection analysis, and the duration of these segments are used to quantify PL intermittency. The results presented here demonstrate that two populations of DCF exist in KAP, with one population demonstrating single-exponential excited state decay over the course of the blinking trace, and the other demonstrating stretched-exponential decay. Molecules demonstrating single-exponential decay also demonstrate modest intensity variation in the blinking trace. Correlation of the emission intensity and excited-state lifetimes demonstrates that for these molecules spectral diffusion is largely responsible for the evolution in emission intensity. In contrast, molecules demonstrating nonexponential excited-state decay vary in emission intensity. Correlation of the emissive intensities with the excited-state lifetimes demonstrates that these molecules undergo changes in both radiative and nonradiative decay rate constants as well as spectral diffusion. These observations suggest that DCF exists in two environments in KAP differentiated by the propensity for proton-transfer with the surrounding KAP matrix. The results presented here provide further insight into the origin of PL intermittency demonstrated by DCF in KAP and related systems.
“…Under this assumption, the emission from a SM will conform to two intensities, one for emission from the optically prepared state and another when the molecule populates a nonemissive state. However, recent applications of sophisticated algorithms such as change-point detection (CPD) in the analysis of SM emission have shown that multiple intensity states are present. − Why would a SM demonstrate more than a single emission intensity? One explanation is spectral diffusion, environmental fluctuations of the ground-excited state energy gap altering the photoexcitation rate, and subsequently the emission intensity .…”
The connection between photoluminescence (PL) intermittency and excited-state kinetics is explored for 2',7'-dichlorofluorescein (DCF) isolated in crystals of potassium acid phthalate (KAP) using time-tagged, time-resolved, time-correlated single-photon counting (T3R-TCSPC). In this technique, PL intermittency or "blinking" is measured in conjunction with the time of photon arrival relative to photoexcitation, allowing for the correlation of emissive intensities and excited-state decay kinetics of single molecules. The blinking trace is parsed into emissive and nonemissive segments using change-point-detection analysis, and the duration of these segments are used to quantify PL intermittency. The results presented here demonstrate that two populations of DCF exist in KAP, with one population demonstrating single-exponential excited state decay over the course of the blinking trace, and the other demonstrating stretched-exponential decay. Molecules demonstrating single-exponential decay also demonstrate modest intensity variation in the blinking trace. Correlation of the emission intensity and excited-state lifetimes demonstrates that for these molecules spectral diffusion is largely responsible for the evolution in emission intensity. In contrast, molecules demonstrating nonexponential excited-state decay vary in emission intensity. Correlation of the emissive intensities with the excited-state lifetimes demonstrates that these molecules undergo changes in both radiative and nonradiative decay rate constants as well as spectral diffusion. These observations suggest that DCF exists in two environments in KAP differentiated by the propensity for proton-transfer with the surrounding KAP matrix. The results presented here provide further insight into the origin of PL intermittency demonstrated by DCF in KAP and related systems.
“…As the operation of optoelectronic devices requires the application of electric fields (EF), the influence of EF on exciton dynamics in conjugated polymers is of great interest [5]. To better understand the interaction between the EF and organic photonic materials on the molecular level, single-molecule spectroscopy (SMS) is often used, which provides insights into some complex fluctuation phenomena that cannot be observed using standard ensemble techniques [6][7][8].…”
The fluorescence intensity of single squaraine-derived rotaxane dye molecules embedded in a poly(methyl methacrylate) matrix is modulated by a sine electric field, and the Frenkel theory is proposed to explain the phenomenon, according to which the fluorescence intensity is proportional to the probability that the electron escapes from the Coulombic barrier between the molecule and its surrounding electron acceptors.
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