Single-molecule Spectroscopy Data Research Articles

From the molecule to the mole: improving heterogeneous copper catalyzed click chemistry using single molecule spectroscopy.

Single molecule spectroscopy (SMS) inspired the optimization of a heterogeneous 'click' catalyst leading to enhanced yields of the Cu-catalyzed reaction of azides with terminal alkynes. Changes in SMS data after optimization confirm the improvements in catalyst performance.

Is There Elliptic Distortion in the Light Harvesting Complex 2 of Purple Bacteria?

Single molecule spectroscopy (SMS) revealed an unusually large Gap between two major exciton peaks of the B850 unit of light harvesting complex 2 (LH2), which could be explained assuming elliptic distortion or k = 2 symmetry modulation in the site excitation energy. On the basis of extensive simulation of the SMS data and ensemble line shape, we found that uniform modulation of k = 2 symmetry cannot explain the dependence of intensity ratios on the Gap of the two major peaks, which are available from SMS, nor the ensemble line shape. Alternative models of disorder with k = 1 and k = 2 symmetry correlation are shown to reproduce these data reasonably well and can even explain the Gap distribution when it is assumed that the lower major peak in the SMS line shape is an intensity weighted average of k = 1- and k = 0 states.

Effect of Sample Preparation and Excitation Conditions on the Single Molecule Spectroscopy of Conjugated Polymers

Extensive new single molecule spectroscopy (SMS) data on the conjugated polymer MEH-PPV at low temperature were obtained. In particular, the combined effects of sample preparation and excitation condition were explored in detail. The data confirm previous observations from this laboratory that (i) the distribution of emission maxima of single MEH-PPV molecules has a bimodal distribution and (ii) the single molecule emission spectrum of MEH-PPV exhibits few time-dependent fluctuations of the emission intensity, band shape, or spectral maxima. These data also help explain the discrepancy among the various published SMS data on this compound and suggest that environmental impurities, long irradiation times, nearby interfaces, and incomplete data sampling may account for some of the discrepancies among the published data.

A detailed single molecule spectroscopy study of the vibronic states and energy transfer pathways of the conjugated polymer MEH-PPV

The low energy onset of the optically accessible density of electronic states (OADOS) of the conjugated polymer MEH-PPV has been investigated by low temperature fluorescence single molecule spectroscopy (SMS). The first extensive set of high signal-to-noise SMS data have been acquired for MEH-PPV samples as a function of molecular weight confirming the previously reported bimodal energy gap distribution. These data have been acquired under sample and radiation conditions that inhibit photophysical dynamics that have distorted previous SMS studies. A molecule by molecule vibronic analysis has yielded an experimentally determined spectral density of the S 0–S 1 energy gaps for the individual chromophores for MEH-PPV. The SMS data has also led to new insights on the energy transfer pathways for conjugated polymers, and on the molecular nature of the “blue” and “red” sites of conjugated polymers. Finally, a combined analysis of the new SMS data with the previously obtained bulk absorption and emission data for MEH-PPV has offered clear evidence that the low energy onset of the OADOS for MEH-PPV, in analogy to the emission spectral density, confirms the existence of a bimodal energy gap distribution.

Dynamics of amorphous polymers in the temperature region 2– [formula omitted] where the standard model of low-temperature glasses begin to fail: studies by single molecule spectroscopy and comparison with photon echo data

Spectra of single tetra-tert-butylterrylene molecules incorporated in purely amorphous polyisobutylene matrix have been measured at 2, 4.5 and 7 K (244, 381 and 187 molecules, correspondingly). This is a temperature region, where the main assumptions of the standard two-level system (TLS) model of low-temperature glasses begin to be not valid. At T=2 K the main parameters of most of the registered spectra were found to be consistent with the standard TLS model. At T=4.5 and 7 K some deviations from predictions of this model were observed. The detailed analysis reveals that increasing of temperature leads to additional, in comparison with the predictions of the standard TLS model, line broadening of spectral peaks. This additional line broadening was attributed to the influence of quasi-local low-frequency modes (LFMs) of the amorphous matrix in system under study at T=4.5 and 7 K . Distributions of single spectral peak widths of the detected spectra (the line width distributions) have been calculated and compared with the line width distributions simulated for the same system. Comparative analysis of experimental and simulated distributions allows to evaluate the value of LFM contribution at 4.5 and 7 K . The single molecule spectroscopy data were compared with the literature values of inverse optical dephasing times, 1/ πT 2, as measured for the same system by photon echo (S.J. Zilker et al., J. Chem. Phys. 109 (1998) 6780).

Minimal distance between chromophore and two-level systems in amorphous solids: effect on photon echo and single molecule spectroscopy data

We investigated the possible effect of the existence of minimal cutoff distance between two-level system (TLS) and chromophore molecule in glasses on the low-temperature photon echo (PE) and single molecule spectroscopy (SMS) data. Our analysis was based on the tunneling TLS and sudden jump models of glasses. The PE data were considered using the stochastic model of PE in low-temperature glasses as modified by us. Analysis of SMS data was based on the theory of SM line shapes developed by Geva and Skinner [J. Phys. Chem. 101 (1997) 8920]. It was shown that the existence of a minimal approach distance between TLS and chromophore centers results in noticeable changes of the calculated PE and SMS data. These changes increase with increasing of temperature.

Comparison of photon echo, hole burning, and single molecule spectroscopy data on low-temperature dynamics of organic amorphous solids

A joint analysis of spectroscopic data obtained at liquid–helium temperatures by three line-narrowing techniques, photon echo (PE), persistent hole burning (HB), and single molecule spectroscopy (SMS), is presented. Two polymer systems, polyisobutylene (PIB) and polymethylmethacrylate (PMMA), doped with tetra-tert-butylterrylene (TBT) were studied via PE and HB techniques and the results are compared with literature data [R. Kettner et al., J. Phys. Chem. 98, 6671 (1994); B. Kozankiewicz et al., J. Chem. Phys. 101, 9377 (1994)] obtained by SMS. Both systems behave quite differently. In TBT/PIB a rather strong influence of a dispersion of the dephasing time T2 was found which plays only a minor role in TBT/PMMA. We have also measured the temperature dependence of T2 for both systems in a broad temperature range (0.4–22 K). Using these data we separated the two different contributions to the optical dephasing — due to an interaction with two-level systems and due to coupling with local low-frequency modes. The data are compared with calculations using a numerical and a semianalytical model in the presence of a large dispersion of the single molecule parameters. Furthermore, we discuss the differences of the linewidths as measured by different experimental methods.

Temperature-dependent line broadening of chromophores in amorphous solids: Differences between single-molecule spectroscopy and photon echo results

Spectroscopic techniques exhibit different sensitivities for line broadening processes in amorphous solids. Photon echo and hole-burning spectroscopy yield averages over the chromophore ensemble. At low temperatures, the results can usually be fitted with a combination of a power-law term — corresponding to the relaxations of two-level systems- and of an exponentially activated contribution of pseudo-local phonon modes. Single-molecule spectroscopy (SMS). in contrast, can resolve the behavior of single dye molecules and yields a distribution of power laws as well as of activation energies. We compare photon echo results for tetra-tert-butylterrylene (TBT) in polyisobutylene (PIB) with SMS data for the same system. The latter were used to simulate numerically the data which would be obtained in an ensemble-averaging experiment. The results of the numerical calculation can be well fitted without assuming a distribution of parameters.

Dephasing and diffusional linewidths in spectra of doped amorphous solids: Comparison of photon echo and single molecule spectroscopy data for terrylene in polyethylene

Abstract The concept of “homogeneous” spectral linewidths in doped amorphous solids and some possibilities to separate the linewidth parts related to the optical dephasing and spectral diffusion (SD) are discussed. The results of the model calculations of the photon echo (PE) decay under conditions of a large dispersion of homogeneous linewidths are presented. The deviations of the PE decay from an exponential due to this dispersion are discussed. The experimental data on incoherent PE in the terrylene/polyethylene system are presented and compared with literature single molecule spectroscopy (SMS) data. It is shown that in this case the dephasing time dispersion plays an important role for the linewidth distribution in SMS. A simple method for separation of the dephasing and SD linewidths in the SMS, based on intensity saturation effects, is considered. The facilities of this method using some SMS data are demonstrated.