One- and two-photon spectroscopy on single molecules of diphenyloctatetraene

Walser, Daniel; Plakhotnik, Taras; Renn, Alois; Wild, Urs P.

doi:10.1016/s0009-2614(97)00324-2

Cited by 17 publications

(21 citation statements)

References 14 publications

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“…Thus, the linewidth is 26-28 MHz on a short time scale, in agreement with OPE data. OPE spectra do not show spectral dynamics in the time range 10 23 10 2 s. This confirms that the difference between the SM linewidths in OPE and TPE spectra is caused by SD induced by the strong illumination at 888 nm, a hypothesis discussed in [22,23]. The dependence of the SD on the IR power was not studied in this work.…”

Section: Physical Chemistry Laboratory Swiss Federal Institute Of Tesupporting

confidence: 71%

“…This technique, which we call intensity-time-frequency correlation (ITFC) SM spectroscopy, can yield microsecond or even better time resolution with an intrinsic theoretical limit at the luminescence lifetime. The ITFC technique is used for studying dynamics in two-photon excitation (TPE) spectra of DPOT molecules in an n-tetradecane matrix [21], where a significant difference between the linewidths in one-photon excitation (OPE) and TPE spectra was observed and tentatively explained by SD induced by the powerful laser illumination required for TPE [22,23]. This explanation agrees with the significant line broadening observed for OPE data in the presence of infrared illumination [24].…”

supporting

confidence: 61%

“…The spectral feature at 3030 MHz represents a SM line with a width of about 60 MHz, a typical linewidth in TPE spectra [21]. This linewidth is more than twice the average linewidth of 26 MHz measured in SM OPE spectra [23]. In the ITFC spectrum with a time resolution of about 40 ms (inset in Fig.…”

Section: Physical Chemistry Laboratory Swiss Federal Institute Of Tementioning

confidence: 76%

“…The sample was immersed in superfluid He at 1.8 K. The intensity of the weak one-photon emission was measured as a function of the laser frequency. Experimental and spectroscopic details are described in [21,23]. The spectral feature at 3030 MHz represents a SM line with a width of about 60 MHz, a typical linewidth in TPE spectra [21].…”

Section: Physical Chemistry Laboratory Swiss Federal Institute Of Tementioning

confidence: 99%

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Time Resolved Single Molecule Spectroscopy

Plakhotnik¹,

Walser²

1998

Phys. Rev. Lett.

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A new method based on the calculation of autocorrelation functions for spectra measured at a high acquisition rate is developed to study spectral dynamics of single molecules. The technique allows for spectroscopy with time resolutions down to the luminescence lifetime. The method is used to study spectral diffusion in two-photon excitation spectra of diphenyloctatetraene molecules doped in an n-tetradecane crystal matrix. The diffusion is light induced, and is absent in one-photon excitation spectra. It has a "steplike" time behavior, different from gradual diffusion observed in glasses.[ S0031-9007(98) Time resolution in SM spectroscopy is also desirable, for example, to study SM interactions with an environment which cause time dependent resonance frequency changes or so-called spectral diffusion (SD). According to the two-level systems (TLSs) model, which was suggested for amorphous solids [13,14] to explain their acoustic and thermodynamic properties, expanded later to include optical phenomena [15], and confirmed in many experiments [16,17], the environment is imitated by a set of TLSs with flip rates distributed from microhertz to gigahertz. A study of fast dynamics requires high time resolution, but it has been considered impossible to implement high time resolution spectroscopy for SMs so far, because the number of detected photons emitted by a SM is small and to first approximation fluctuates according to a Poisson distribution. Even when the exciting laser power saturates the transition and the emission rate is at maximum, a SM signal rarely reaches 10 5 counts͞s (a strong emitter is terrylene [18]). To measure the SM linewidth, the laser intensity should be well below the saturation value. So, only 10 4 counts͞s are detected. To determine the line shape, the recording time should be on the order of 10 ms in the best case. For molecules with 100 times lower emission rate [pentacene, diphenyloctatetraene (DPOT), and many others], this time can be as long as a few seconds. A conventional photon correlation technique [19,20] allows one to gain insight into fast SM dynamics but does not provide spectral information.In this paper, a new approach to SM spectroscopy is reported which pushes the time resolution far below one second, even for molecules with poor emission rates. This technique, which we call intensity-time-frequency correlation (ITFC) SM spectroscopy, can yield microsecond or even better time resolution with an intrinsic theoretical limit at the luminescence lifetime. The ITFC technique is used for studying dynamics in two-photon excitation (TPE) spectra of DPOT molecules in an n-tetradecane matrix [21], where a significant difference between the linewidths in one-photon excitation (OPE) and TPE spectra was observed and tentatively explained by SD induced by the powerful laser illumination required for TPE [22,23]. This explanation agrees with the significant line broadening observed for OPE data in the presence of infrared illumination [24].ITFC spectroscopy works as follows. Instead of record...

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Section: Physical Chemistry Laboratory Swiss Federal Institute Of Tesupporting

confidence: 71%

supporting

confidence: 61%

Section: Physical Chemistry Laboratory Swiss Federal Institute Of Tementioning

confidence: 76%

Section: Physical Chemistry Laboratory Swiss Federal Institute Of Tementioning

confidence: 99%

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Time Resolved Single Molecule Spectroscopy

Plakhotnik¹,

Walser²

1998

Phys. Rev. Lett.

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“…[25][26][27][28][29] The combination of one-and two-photon excitation studies has shown that the right choice of a guest-host system is crucial in singlemolecule spectroscopy because the electronic excited-state properties depend sensitively on the host species. For instance, the replacement of the host molecule by its predeuterated form may lead to significant changes in the single molecule spectra.…”

Section: Introductionmentioning

confidence: 99%

Symmetry breaking and spectra of diphenyloctatetraene in n-alkanes

Walser

Zumofen

Plakhotnik

2000

The Journal of Chemical Physics

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Articles you may be interested inElectronic spectra of azaindole and its excited state mixing: A symmetry-adapted cluster configuration interaction study J. Chem. Phys. 143, 204304 (2015); 10.1063/1.4935578The elusive S 2 state, the S 1/S 2 splitting, and the excimer states of the benzene dimer J. Chem. Phys. 142, 234306 (2015) One-and two-photon excitation spectra, as well as absorption and emission spectra of diphenyloctatetraene ͑DPOT͒ in n-alkanes are investigated at low temperatures. For DPOT in n-octane we report on the measurements of one-photon excitation and emission spectra and for DPOT in n-tetradecane ͑TD͒ on the measurements of one-and two-photon excitation spectra and emission spectra. The spectra are governed by the transitions between the electronic ground (S 0 ) and the two lowest electronic excited singlet states (S 1 ,S 2 ). The interpretation is based on allowed transitions and transitions induced by the S 1 -S 2 coupling due to Herzberg-Teller promoting modes or due to static lattice-induced distortions of DPOT. A single noncentrosymmetric site is observed for DPOT in n-octane. For DPOT in TD a centrosymmetric and a noncentrosymmetric site are reported. The analysis indicates that there is a dynamical equilibrium in the population of these two sites. The experimental data are quantitatively studied by comparison with simulated spectra. The simulation calculations are based on the coupling between nonadiabatic S 1 and S 2 states, harmonic modes, and suitable transition moments and line-shape functions. For DPOT in TD the calculations reveal an interesting interference pattern in the vibronic progressions observed in two-photon excitation spectra.

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On the photophysical model for polyenes: Experimental evidence of the 1,8‐diphenylocta‐1,3,5,7‐tetraene molecule dissolved in n‐octane, cyclooctane, and 2,2,4‐trimethylpentane

Catalán

2017

J of Physical Organic Chem

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Spectroscopic evidence recorded in solutions of diphenyloctatetraene in n‐octane, cyclooctane, and 2,2,4‐trimethylpentane by sudden immersion of the sample at 77 K or by changing the solution temperature slowly between 293 and 77 K allow us to conclude that the distinct spectroscopic behavior of the polyene compounds, on extending its polyene chain, does not lie in the existence of a ghost state 21Ag, as first excited electronic state of the system, but resides in a structural problem that influences whether its first electronic transition for absorption can be monitored or not at its lowest vibrational levels.

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One- and two-photon spectroscopy on single molecules of diphenyloctatetraene

Cited by 17 publications

References 14 publications

Time Resolved Single Molecule Spectroscopy

Time Resolved Single Molecule Spectroscopy

Symmetry breaking and spectra of diphenyloctatetraene in n-alkanes

On the photophysical model for polyenes: Experimental evidence of the 1,8‐diphenylocta‐1,3,5,7‐tetraene molecule dissolved in n‐octane, cyclooctane, and 2,2,4‐trimethylpentane

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