Spectroscopy of 3, 4, 9, 10-perylenetetracarboxylic dianhydride (PTCDA) attached to rare gas samples: Clusters vs. bulk matrices. II. Fluorescence emission spectroscopy

Dvořák, Matthieu; Müller, Markus; Knoblauch, Tobias; Bünermann, Oliver; Rydlo, A.; Minniberger, Stefan; Harbich, W.; Stienkemeier, F.

doi:10.1063/1.4759445

Cited by 14 publications

(13 citation statements)

References 30 publications

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“…29.) The energies of all these vibrational modes are very similar to those measured for PTCDA by Stienkemeier and coworkers, 14,16 using the helium nanodroplet isolation technique. 46 Taken all together, this demonstrates that the modes above 230 cm À1 do not couple to substrate phonons and are thus not modified by the substrate bonding.…”

Section: Resultssupporting

confidence: 79%

Surface induced vibrational modes in the fluorescence spectra of PTCDA adsorbed on the KCl(100) and NaCl(100) surfaces

Paulheim

Marquardt

Sokołowski

et al. 2016

Phys. Chem. Chem. Phys.

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We report a combined experiment-theory study on low energy vibrational modes in fluorescence spectra of perylene-3,4,9,10-tetracarboxylic acid dianhydride (PTCDA) molecules. Using very low coverages, isolated molecules were adsorbed on terrace sites or at sites located at residual steps on (100) oriented alkali halide films (KCl and NaCl). The low energy modes couple to the optical transition only because the PTCDA molecule is geometrically distorted (C) upon adsorption on the surface; they would be absent for the parent planar (D) PTCDA molecule. The modes differ in number and energy for molecules adsorbed on regular terrace sites and molecules adsorbed at step edge sites. Modes appearing for step edge sites have the character of frustrated rotations. Their coupling to the optical transition is a consequence of the further reduced symmetry of the step edge sites. We find a larger number of vibrational modes on NaCl than on KCl. We explain this by the stronger electrostatic bonding of the PTCDA on NaCl compared to KCl. It causes the optical transition to induce stronger changes in the molecular coordinates, thus leading to larger Franck-Condon factors and thus stronger coupling. Our results demonstrate how optical spectroscopy can be used to gain information on adsorption sites of molecules at low surface concentrations.

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Section: Resultssupporting

confidence: 79%

Surface induced vibrational modes in the fluorescence spectra of PTCDA adsorbed on the KCl(100) and NaCl(100) surfaces

Paulheim

Marquardt

Sokołowski

et al. 2016

Phys. Chem. Chem. Phys.

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show abstract

“…Furthermore, the weak interaction with the helium leads to a very small perturbation and is the reason for the observed narrow spectral lines. 48,49 The comparison of the experimental and the calculated vibronic spectrum shows a quantitative agreement, but it also reveals a systematic error. The calculated vibrational energies are systematically overestimating the experimental vibrational energies.…”

Section: ■ Introductionmentioning

confidence: 72%

“…As a starting and reference point we calculated the vibrations and the resulting FCFs of the D 2h -symmetric PTCDA molecule in the gas phase. Experimental reference data are available from a previous study by Stienkemeier et al, who measured the fluorescence spectrum of PTCDA in ultracold He nanodroplets (400 mK) 48 which leads to a very good resolution of the vibrational fine structure. Almost exclusively the vibrational ground state of the S 1 state is populated which leads to a simplification of the vibronic spectrum because the number of hot bands is very low.…”

Section: ■ Introductionmentioning

confidence: 99%

Analysis of the Vibronic Spectra of Perylene-3,4,9,10-tetracarboxylic Dianhydride Adsorbed on NaCl and KCl

et al. 2016

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The vibrational fine structure of the fluorescence spectra of isolated perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) molecules adsorbed on (100) surfaces of sodium chloride and potassium chloride has been studied theoretically and experimentally. In order to analyze the experimentally observed differences in the vibronic spectra of PTCDA adsorbed on the two surfaces, we simulated the spectra by calculating the Franck−Condon factors. The calculated spectra are in excellent agreement with the experiment and indicate that the difference between the two surfaces is the result of a stronger distortion of the molecular geometry on NaCl.

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“…1 In this paper, we report on FL spectra for isolated entities of the dye molecule perylene-3,4,9,10-tetracarboxyl acid dianhydride (PTCDA). [5][6][7] A very small surface concentration (named as coverage in the following) of PTCDA was deposited on thin (100) oriented films of KCl. These films were epitaxially grown on a Ag(100) single crystal surface.…”

Section: Introductionmentioning

confidence: 99%

Fluorescence spectroscopy of PTCDA molecules on the KCl(100) surface in the limit of low coverages: site selection and diffusion

Paulheim

Müller

Marquardt

et al. 2013

Phys. Chem. Chem. Phys.

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We performed fluorescence (FL) and fluorescence excitation (FLE) spectroscopy on the model molecule perylene-3,4,9,10-tetracarboxyl acid dianhydride (PTCDA) for very low coverages (below 1% of a monolayer) on thin (100) oriented KCl films. Two different states of PTCDA molecules can be distinguished in the spectra: an initial state, which is observed directly after deposition of the molecules onto the cold sample at 20 K, and a final state, which is found after intensive optical excitation or thermal annealing of the sample. The spectrum of the final state is blue-shifted with respect to that of the initial state by 130 ± 15 cm(-1) and exhibits lines with significantly reduced widths. This can be explained by diffusion of molecules from initially populated terrace sites to energetically favoured step edge sites. Polarization dependent spectroscopy reveals the same azimuthal orientation of the molecules on both adsorption sites and leads to a model of the adsorption geometry of PTCDA at the KCl step sites. Our experiment demonstrates how optical spectroscopy can be used to investigate kinetic processes of fluorescent molecules on surfaces.

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Spectroscopy of 3, 4, 9, 10-perylenetetracarboxylic dianhydride (PTCDA) attached to rare gas samples: Clusters vs. bulk matrices. II. Fluorescence emission spectroscopy

Cited by 14 publications

References 30 publications

Surface induced vibrational modes in the fluorescence spectra of PTCDA adsorbed on the KCl(100) and NaCl(100) surfaces

Surface induced vibrational modes in the fluorescence spectra of PTCDA adsorbed on the KCl(100) and NaCl(100) surfaces

Analysis of the Vibronic Spectra of Perylene-3,4,9,10-tetracarboxylic Dianhydride Adsorbed on NaCl and KCl

Fluorescence spectroscopy of PTCDA molecules on the KCl(100) surface in the limit of low coverages: site selection and diffusion

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