2017
|
| 13. | P. Puschnig, A. D. Boese, M. Willenbockel, M. Meyer, D. Lüftner, E. M. Reinisch, T. Ules, G. Koller, S. Soubatch, M. G. Ramsey, F. S. Tautz Energy ordering of molecular orbitals Journal Article In: J. Phys. Chem. Lett., vol. 8, pp. 208-213, 2017. @article{Puschnig2016,
title = {Energy ordering of molecular orbitals},
author = {P. Puschnig and A. D. Boese and M. Willenbockel and M. Meyer and D. Lüftner and E. M. Reinisch and T. Ules and G. Koller and S. Soubatch and M. G. Ramsey and F. S. Tautz},
doi = {10.1021/acs.jpclett.6b02517},
year = {2017},
date = {2017-01-01},
journal = {J. Phys. Chem. Lett.},
volume = {8},
pages = {208-213},
abstract = {Orbitals are invaluable in providing a model of bonding in molecules or between molecules and surfaces. Most present-day methods in computational chemistry begin by calculating the molecular orbitals of the system. To what extent have these mathematical objects analogues in the real world? To shed light on this intriguing question, we employ a photoemission tomography study on monolayers of 3,4,9,10-perylene-tetracarboxylic acid dianhydride (PTCDA) grown on three Ag surfaces. The characteristic photoelectron angular distribution enables us to assign individual molecular orbitals to the emission features. When comparing the resulting energy positions to density functional calculations, we observe deviations in the energy ordering. By performing complete active space calculations (CASSCF), we can explain the experimentally observed orbital ordering, suggesting the importance of static electron correlation beyond a (semi)local approximation. On the other hand, our results also show reality and robustness of the orbital concept, thereby making molecular orbitals accessible to experimental observations.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Orbitals are invaluable in providing a model of bonding in molecules or between molecules and surfaces. Most present-day methods in computational chemistry begin by calculating the molecular orbitals of the system. To what extent have these mathematical objects analogues in the real world? To shed light on this intriguing question, we employ a photoemission tomography study on monolayers of 3,4,9,10-perylene-tetracarboxylic acid dianhydride (PTCDA) grown on three Ag surfaces. The characteristic photoelectron angular distribution enables us to assign individual molecular orbitals to the emission features. When comparing the resulting energy positions to density functional calculations, we observe deviations in the energy ordering. By performing complete active space calculations (CASSCF), we can explain the experimentally observed orbital ordering, suggesting the importance of static electron correlation beyond a (semi)local approximation. On the other hand, our results also show reality and robustness of the orbital concept, thereby making molecular orbitals accessible to experimental observations. |
2016
|
| 12. | E. M. Reinisch, P. Puschnig, T. Ules, M. G. Ramsey, G. Koller Layer-resolved photoemission tomography: The $p$-sexiphenyl bilayer upon Cs doping Journal Article In: Phys. Rev. B, vol. 93, iss. 15, pp. 155438, 2016. @article{Reinisch2016,
title = {Layer-resolved photoemission tomography: The $p$-sexiphenyl bilayer upon Cs doping},
author = {E. M. Reinisch and P. Puschnig and T. Ules and M. G. Ramsey and G. Koller},
doi = {10.1103/PhysRevB.93.155438},
year = {2016},
date = {2016-04-01},
journal = {Phys. Rev. B},
volume = {93},
issue = {15},
pages = {155438},
abstract = {The buried interface between a molecular thin film and the metal substrate is generally not accessible to the photoemission experiment. With the example of a sexiphenyl (6P) bilayer on Cu we show that photoemission tomography can be used to study the electronic level alignment and geometric structure, where it was possible to assign the observed orbital emissions to the individual layers. We further study the Cs doping of this bilayer. Initial Cs exposure leads to a doping of only the first interface layer, leaving the second layer unaffected except for a large energy shift. This result shows that it is in principle possible to chemically modify just the interface, which is important to issues like tuning of the energy level alignment and charge transfer to the interface layer. Upon saturating the film with Cs, photoemission tomography shows a complete doping (6p4−) of the bilayer, with the molecular geometry changing such that the spectra become dominated by σ-orbital emissions.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The buried interface between a molecular thin film and the metal substrate is generally not accessible to the photoemission experiment. With the example of a sexiphenyl (6P) bilayer on Cu we show that photoemission tomography can be used to study the electronic level alignment and geometric structure, where it was possible to assign the observed orbital emissions to the individual layers. We further study the Cs doping of this bilayer. Initial Cs exposure leads to a doping of only the first interface layer, leaving the second layer unaffected except for a large energy shift. This result shows that it is in principle possible to chemically modify just the interface, which is important to issues like tuning of the energy level alignment and charge transfer to the interface layer. Upon saturating the film with Cs, photoemission tomography shows a complete doping (6p4−) of the bilayer, with the molecular geometry changing such that the spectra become dominated by σ-orbital emissions. |
| 11. | T. Ules, D. Lüftner, E. M. Reinisch, G. Koller, P. Puschnig, M. G. Ramsey Continuous or discrete: Tuning the energy level alignment of organic layers with alkali dopants Journal Article In: Phys. Rev. B, vol. 94, pp. 205405, 2016. @article{Ules2016,
title = {Continuous or discrete: Tuning the energy level alignment of organic layers with alkali dopants},
author = {T. Ules and D. Lüftner and E. M. Reinisch and G. Koller and P. Puschnig and M. G. Ramsey},
doi = {10.1103/PhysRevB.94.205405},
year = {2016},
date = {2016-01-01},
journal = {Phys. Rev. B},
volume = {94},
pages = {205405},
abstract = {This paper investigates the effects of cesium (Cs) deposited on pentacene (5A) and sexiphenyl (6P) monolayers on the Ag(110) substrate. The process of doping and the energy level alignment are studied quantitatively and contrasted. While ultimately for both molecules lowest unoccupied molecular orbital (LUMO) filling on charge transfer upon Cs dosing is observed, the doping processes are tellingly different. In the case of 5A, hybrid molecule-substrate states and doping states coexist at lowest Cs exposures, while for 6P doping states appear only after Cs has completely decoupled the monolayer from the substrate. With the support of density functional theory calculations, this different behavior is rationalized by the local character of electrostatic potential changes induced by dopants in relation to the spatial extent of the molecules. This also has severe effects on the energy level alignment, which for most dopant/molecule systems cannot be considered continuous but discrete.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
This paper investigates the effects of cesium (Cs) deposited on pentacene (5A) and sexiphenyl (6P) monolayers on the Ag(110) substrate. The process of doping and the energy level alignment are studied quantitatively and contrasted. While ultimately for both molecules lowest unoccupied molecular orbital (LUMO) filling on charge transfer upon Cs dosing is observed, the doping processes are tellingly different. In the case of 5A, hybrid molecule-substrate states and doping states coexist at lowest Cs exposures, while for 6P doping states appear only after Cs has completely decoupled the monolayer from the substrate. With the support of density functional theory calculations, this different behavior is rationalized by the local character of electrostatic potential changes induced by dopants in relation to the spatial extent of the molecules. This also has severe effects on the energy level alignment, which for most dopant/molecule systems cannot be considered continuous but discrete. |
2015
|
| 10. | H. Offenbacher, D. Lüftner, T. Ules, E. M. Reinisch, G. Koller, P. Puschnig, M. G. Ramsey Orbital tomography: molecular band maps, momentum maps and the imaging of real space orbitals of adsorbed molecules Journal Article In: J. Elec. Spec. Relat. Phenom., vol. 204A, pp. 92-101, 2015. @article{Ramsey2015,
title = {Orbital tomography: molecular band maps, momentum maps and the imaging of real space orbitals of adsorbed molecules},
author = {H. Offenbacher and D. Lüftner and T. Ules and E. M. Reinisch and G. Koller and P. Puschnig and M. G. Ramsey},
doi = {10.1016/j.elspec.2015.04.023},
year = {2015},
date = {2015-01-01},
journal = {J. Elec. Spec. Relat. Phenom.},
volume = {204A},
pages = {92-101},
abstract = {The frontier orbitals of molecules are the prime determinants of their chemical, optical and electronic properties. Arguably, the most direct method of addressing the (filled) frontier orbitals is ultra-violet photoemission spectroscopy (UPS). Although UPS is a mature technique from the early 1970s on, the angular distribution of the photoemitted electrons was thought to be too complex to be analysed quantitatively. Recently angle resolved UPS (ARUPS) work on conjugated molecules both, in ordered thick films and chemisorbed monolayers, has shown that the angular (momentum) distribution of the photocurrent from orbital emissions can be simply understood. The approach, based on the assumption of a plane wave final state is becoming known as orbital tomography. Here we will demonstrate, with selected examples of pentacene (5A) and sexiphenyl (6P), the potential of orbital tomography. First it will be shown how the full angular distribution of the photocurrent (momentum map) from a specific orbital is related to the real space orbital by a Fourier transform. Examples of the reconstruction of 5A orbitals will be given and the procedure for recovering the lost phase information will be outlined. We then move to examples of sexiphenyl where we interrogate the original band maps of thick sexiphenyl in the light of our understanding of orbital tomography that has developed since then. With comparison to theoretical simulations of the molecular band maps, the molecular conformation and orientation will be concluded. New results for the sexiphenyl monolayer on Al(1 1 0) will then be presented. From the band maps it will be concluded that the molecule is planarised and adopts a tilted geometry. Finally the momentum maps down to HOMO-11 will be analysed and real space orbitals reconstructed.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The frontier orbitals of molecules are the prime determinants of their chemical, optical and electronic properties. Arguably, the most direct method of addressing the (filled) frontier orbitals is ultra-violet photoemission spectroscopy (UPS). Although UPS is a mature technique from the early 1970s on, the angular distribution of the photoemitted electrons was thought to be too complex to be analysed quantitatively. Recently angle resolved UPS (ARUPS) work on conjugated molecules both, in ordered thick films and chemisorbed monolayers, has shown that the angular (momentum) distribution of the photocurrent from orbital emissions can be simply understood. The approach, based on the assumption of a plane wave final state is becoming known as orbital tomography. Here we will demonstrate, with selected examples of pentacene (5A) and sexiphenyl (6P), the potential of orbital tomography. First it will be shown how the full angular distribution of the photocurrent (momentum map) from a specific orbital is related to the real space orbital by a Fourier transform. Examples of the reconstruction of 5A orbitals will be given and the procedure for recovering the lost phase information will be outlined. We then move to examples of sexiphenyl where we interrogate the original band maps of thick sexiphenyl in the light of our understanding of orbital tomography that has developed since then. With comparison to theoretical simulations of the molecular band maps, the molecular conformation and orientation will be concluded. New results for the sexiphenyl monolayer on Al(1 1 0) will then be presented. From the band maps it will be concluded that the molecule is planarised and adopts a tilted geometry. Finally the momentum maps down to HOMO-11 will be analysed and real space orbitals reconstructed. |
| 9. | S. Weiß, D. Lüftner, T. Ules, E. M. Reinisch, H. Kaser, A. Gottwald, M. Richter, S. Soubatch, G. Koller, M. G. Ramsey, F. S. Tautz, P. Puschnig Exploring three-dimensional orbital imaging with energy-dependent photoemission tomography Journal Article In: Nat. Commun., vol. 6, pp. 8287, 2015. @article{Weiss2015,
title = {Exploring three-dimensional orbital imaging with energy-dependent photoemission tomography},
author = {S. Weiß and D. Lüftner and T. Ules and E. M. Reinisch and H. Kaser and A. Gottwald and M. Richter and S. Soubatch and G. Koller and M. G. Ramsey and F. S. Tautz and P. Puschnig},
doi = {10.1038/ncomms9287},
year = {2015},
date = {2015-01-01},
journal = {Nat. Commun.},
volume = {6},
pages = {8287},
abstract = {Recently, it has been shown that experimental data from angle-resolved photoemission spectroscopy on oriented molecular films can be utilized to retrieve real-space images of molecular orbitals in two dimensions. Here, we extend this orbital tomography technique by performing photoemission initial state scans as a function of photon energy on the example of the brickwall monolayer of 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) on Ag(110). The overall dependence of the photocurrent on the photon energy can be well accounted for by assuming a plane wave for the final state. However, the experimental data, both for the highest occupied and the lowest unoccupied molecular orbital of PTCDA, exhibits an additional modulation attributed to final state scattering effects. Nevertheless, as these effects beyond a plane wave final state are comparably small, we are able, with extrapolations beyond the attainable photon energy range, to reconstruct three-dimensional images for both orbitals in agreement with calculations for the adsorbed molecule.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Recently, it has been shown that experimental data from angle-resolved photoemission spectroscopy on oriented molecular films can be utilized to retrieve real-space images of molecular orbitals in two dimensions. Here, we extend this orbital tomography technique by performing photoemission initial state scans as a function of photon energy on the example of the brickwall monolayer of 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) on Ag(110). The overall dependence of the photocurrent on the photon energy can be well accounted for by assuming a plane wave for the final state. However, the experimental data, both for the highest occupied and the lowest unoccupied molecular orbital of PTCDA, exhibits an additional modulation attributed to final state scattering effects. Nevertheless, as these effects beyond a plane wave final state are comparably small, we are able, with extrapolations beyond the attainable photon energy range, to reconstruct three-dimensional images for both orbitals in agreement with calculations for the adsorbed molecule. |
| 8. | E. M. Reinisch n-Doping of Conjugated Molecules on fcc Metal Surfaces: Investigations employing Photoemission PhD Thesis 2015. @phdthesis{Reinisch2015,
title = {n-Doping of Conjugated Molecules on fcc Metal Surfaces: Investigations employing Photoemission},
author = {E. M. Reinisch},
url = {https://resolver.obvsg.at/urn:nbn:at:at-ubg:1-87992},
year = {2015},
date = {2015-01-01},
urldate = {2015-01-01},
abstract = {In this thesis investigations of the electronic and geometric structure of ordered organic semiconductor thin films upon alkali metal exposure are presented. The aims of this work were (i) the characterization of doping states (former unoccupied electronic states) in the band gap region of the conjugated molecules upon increasing Cs exposure, and (ii) the determination of the molecular orientation and conformation (i.e. tilt and twist). Within this framework a method called “Photoemission Tomography” (also known as “Orbital Tomography”) is demonstrated, which is based on a combination of angle-resolved UV-photoemission spectroscopy (ARUPS) data and DFT simulations. Fundamental for the identification of molecular orbitals is the correlation between the real space structure (initial state) and the photoelectron intensity distribution in momentum space (final state), which can be approximated by assuming the final state as a simple plane wave. The investigations concerned the adsorption of the conjugated molecules Sexiphenyl (6P), Pentaphenyl (5P) and Sexithiophene (6T) on different fcc metal substrates in the pristine and Cs-exposed states. The 6P monolayer Cu(110) acts as exemplary adsorption system is this thesis. Here, the former hybridized molecules become decoupled (tilted) and then doped (filling of the LUMO, then LUMO+1) upon increasing Cs deposition. This is also observed for the first layer in the 6P bilayer on Cu(110), where the second layer just becomes tilted but not doped. On the Ag(110), Ag(100) and Ag(111) faces 6P orients differently according to the substrate symmetries. Upon Cs exposure the molecules reorient (ranging from simple reorientation to rotational disorder for different surfaces) on all Ag faces but remain ordered. 5P contains an odd number of phenyl rings in contrast to 6P. Nevertheless its adsorption and doping development is similar to 6P.},
keywords = {},
pubstate = {published},
tppubtype = {phdthesis}
}
In this thesis investigations of the electronic and geometric structure of ordered organic semiconductor thin films upon alkali metal exposure are presented. The aims of this work were (i) the characterization of doping states (former unoccupied electronic states) in the band gap region of the conjugated molecules upon increasing Cs exposure, and (ii) the determination of the molecular orientation and conformation (i.e. tilt and twist). Within this framework a method called “Photoemission Tomography” (also known as “Orbital Tomography”) is demonstrated, which is based on a combination of angle-resolved UV-photoemission spectroscopy (ARUPS) data and DFT simulations. Fundamental for the identification of molecular orbitals is the correlation between the real space structure (initial state) and the photoelectron intensity distribution in momentum space (final state), which can be approximated by assuming the final state as a simple plane wave. The investigations concerned the adsorption of the conjugated molecules Sexiphenyl (6P), Pentaphenyl (5P) and Sexithiophene (6T) on different fcc metal substrates in the pristine and Cs-exposed states. The 6P monolayer Cu(110) acts as exemplary adsorption system is this thesis. Here, the former hybridized molecules become decoupled (tilted) and then doped (filling of the LUMO, then LUMO+1) upon increasing Cs deposition. This is also observed for the first layer in the 6P bilayer on Cu(110), where the second layer just becomes tilted but not doped. On the Ag(110), Ag(100) and Ag(111) faces 6P orients differently according to the substrate symmetries. Upon Cs exposure the molecules reorient (ranging from simple reorientation to rotational disorder for different surfaces) on all Ag faces but remain ordered. 5P contains an odd number of phenyl rings in contrast to 6P. Nevertheless its adsorption and doping development is similar to 6P. |
2014
|
| 7. | D. Lüftner, T. Ules, E. M. Reinisch, G. Koller, S. Soubatch, F. S. Tautz, M. G. Ramsey, P. Puschnig Imaging the wave functions of adsorbed molecules Journal Article In: PNAS, vol. 111, no. 2, pp. 605-610, 2014. @article{Luftner2013,
title = {Imaging the wave functions of adsorbed molecules},
author = {D. Lüftner and T. Ules and E. M. Reinisch and G. Koller and S. Soubatch and F. S. Tautz and M. G. Ramsey and P. Puschnig},
doi = {10.1073/pnas.1315716110},
year = {2014},
date = {2014-01-01},
journal = {PNAS},
volume = {111},
number = {2},
pages = {605-610},
abstract = {In quantum mechanics, the electrons in a molecule are described by a mathematical object termed the wave function or molecular orbital. This function determines the chemical and physical properties of matter and consequently there has been much interest in measuring orbitals, despite the fact that strictly speaking they are not quantum-mechanical observables. We show how the amplitude and phase of orbitals can be measured in good agreement with wave functions from ab initio calculations. Not only do such measurements allow wave functions of complex molecules and nanostructures to be determined, they also open up a window into critical discussions of theoretical orbital concepts.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
In quantum mechanics, the electrons in a molecule are described by a mathematical object termed the wave function or molecular orbital. This function determines the chemical and physical properties of matter and consequently there has been much interest in measuring orbitals, despite the fact that strictly speaking they are not quantum-mechanical observables. We show how the amplitude and phase of orbitals can be measured in good agreement with wave functions from ab initio calculations. Not only do such measurements allow wave functions of complex molecules and nanostructures to be determined, they also open up a window into critical discussions of theoretical orbital concepts. |
| 6. | E. M. Reinisch, T. Ules, P. Puschnig, S. Berkebile, M. Ostler, T. Seyller, M. G. Ramsey, G. Koller Development and character of gap states on alkali doping of molecular films Journal Article In: New J. Phys., vol. 16, pp. 023011, 2014. @article{Reinisch2013,
title = {Development and character of gap states on alkali doping of molecular films},
author = {E. M. Reinisch and T. Ules and P. Puschnig and S. Berkebile and M. Ostler and T. Seyller and M. G. Ramsey and G. Koller},
doi = {10.1088/1367-2630/16/2/023011},
year = {2014},
date = {2014-01-01},
journal = {New J. Phys.},
volume = {16},
pages = {023011},
abstract = {Here we study the alkali metal induced effects on an ordered and aligned sexiphenyl monolayer on Cu(110) with angle-resolved UV spectroscopy (ARUPS). The caesium (Cs) induced gap states could clearly be identified by orbital tomography, a method based on ARUPS, which allows both the orbital character of these states and the molecular orientation to be determined. We show that with increasing alkali metal dose, doping proceeds in three distinct steps. Initially, Cs decouples the molecular monolayer from the substrate, with emptying of the lowest unoccupied molecular orbital (LUMO) that had been filled on hybridization with the substrate. Further Cs exposure refills the LUMO. Finally a filling of the LUMO+1 by charge transfer from the alkali metal occurs. Remarkably, although long range order is not preserved and the molecular planes tilt away from the surface, the molecules remain aligned parallel to the $[1 bar 1 0]$ azimuth during the whole doping process.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Here we study the alkali metal induced effects on an ordered and aligned sexiphenyl monolayer on Cu(110) with angle-resolved UV spectroscopy (ARUPS). The caesium (Cs) induced gap states could clearly be identified by orbital tomography, a method based on ARUPS, which allows both the orbital character of these states and the molecular orientation to be determined. We show that with increasing alkali metal dose, doping proceeds in three distinct steps. Initially, Cs decouples the molecular monolayer from the substrate, with emptying of the lowest unoccupied molecular orbital (LUMO) that had been filled on hybridization with the substrate. Further Cs exposure refills the LUMO. Finally a filling of the LUMO+1 by charge transfer from the alkali metal occurs. Remarkably, although long range order is not preserved and the molecular planes tilt away from the surface, the molecules remain aligned parallel to the $[1 bar 1 0]$ azimuth during the whole doping process. |
| 5. | B. Stadtmüller, D. Lüftner, M. Willenbockel, E. M. Reinisch, T. Sueyoshi, G. Koller, S. Soubatch, M. G. Ramsey, P. Puschnig, F. S. Tautz, C. Kumpf Unexpected interplay of bonding height and energy level alignment at heteromolecular hybrid interfaces Journal Article In: Nat. Commun., vol. 5, pp. 3685, 2014. @article{Stadtmuller2013,
title = {Unexpected interplay of bonding height and energy level alignment at heteromolecular hybrid interfaces},
author = {B. Stadtmüller and D. Lüftner and M. Willenbockel and E. M. Reinisch and T. Sueyoshi and G. Koller and S. Soubatch and M. G. Ramsey and P. Puschnig and F. S. Tautz and C. Kumpf},
doi = {10.1038/ncomms4685},
year = {2014},
date = {2014-01-01},
journal = {Nat. Commun.},
volume = {5},
pages = {3685},
abstract = {Although geometric and electronic properties of any physical or chemical system are always mutually coupled by the rules of quantum mechanics, counterintuitive coincidences between the two are sometimes observed. The coadsorption of the organic molecules 3,4,9,10-perylene tetracarboxylic dianhydride and copper-II-phthalocyanine on Ag(111) represents such a case, since geometric and electronic structures appear to be decoupled: one molecule moves away from the substrate while its electronic structure indicates a stronger chemical interaction, and vice versa for the other. Our comprehensive experimental and ab-initio theoretical study reveals that, mediated by the metal surface, both species mutually amplify their charge-donating and -accepting characters, respectively. This resolves the apparent paradox, and demonstrates with exceptional clarity how geometric and electronic bonding parameters are intertwined at metal–organic interfaces.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Although geometric and electronic properties of any physical or chemical system are always mutually coupled by the rules of quantum mechanics, counterintuitive coincidences between the two are sometimes observed. The coadsorption of the organic molecules 3,4,9,10-perylene tetracarboxylic dianhydride and copper-II-phthalocyanine on Ag(111) represents such a case, since geometric and electronic structures appear to be decoupled: one molecule moves away from the substrate while its electronic structure indicates a stronger chemical interaction, and vice versa for the other. Our comprehensive experimental and ab-initio theoretical study reveals that, mediated by the metal surface, both species mutually amplify their charge-donating and -accepting characters, respectively. This resolves the apparent paradox, and demonstrates with exceptional clarity how geometric and electronic bonding parameters are intertwined at metal–organic interfaces. |
| 4. | T. Ules, D. Lüftner, E. M. Reinisch, G. Koller, P. Puschnig, M. G. Ramsey Orbital Tomography of Hybridized and Dispersing Molecular Overlayers Journal Article In: Phys. Rev. B, vol. 90, pp. 155430, 2014. @article{Ules2014,
title = {Orbital Tomography of Hybridized and Dispersing Molecular Overlayers},
author = {T. Ules and D. Lüftner and E. M. Reinisch and G. Koller and P. Puschnig and M. G. Ramsey},
doi = {10.1103/PhysRevB.90.155430},
year = {2014},
date = {2014-01-01},
journal = {Phys. Rev. B},
volume = {90},
pages = {155430},
abstract = {With angle-resolved photoemission experiments and ab initio electronic structure calculations, the pentacene monolayers on Ag(110) and Cu(110) are compared and contrasted, allowing the molecular orientation to be determined and an unambiguous assignment of emissions to specific orbitals to be made. On Ag(110), the orbitals remain essentially isolated-molecule-like, while strong substrate-enhanced dispersion and orbital modification are observed upon adsorption on Cu(110). We show how the photoemission intensity of extended systems can be simulated and that it behaves essentially like that of the isolated molecule modulated by the band dispersion due to intermolecular interactions.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
With angle-resolved photoemission experiments and ab initio electronic structure calculations, the pentacene monolayers on Ag(110) and Cu(110) are compared and contrasted, allowing the molecular orientation to be determined and an unambiguous assignment of emissions to specific orbitals to be made. On Ag(110), the orbitals remain essentially isolated-molecule-like, while strong substrate-enhanced dispersion and orbital modification are observed upon adsorption on Cu(110). We show how the photoemission intensity of extended systems can be simulated and that it behaves essentially like that of the isolated molecule modulated by the band dispersion due to intermolecular interactions. |
2013
|
| 3. | M. Willenbockel, B. Stadtmüller, K. Schönauer, F. C. Bocquet, D. Lüftner, E. M. Reinisch, T. Ules, G. Koller, C. Kumpf, S. Soubatch, P. Puschnig, M. G. Ramsey, F. S. Tautz Energy offsets within a molecular monolayer: The influence of the molecular environment Journal Article In: New J. Phys., vol. 15, pp. 033017, 2013. @article{Willenbockel2012,
title = {Energy offsets within a molecular monolayer: The influence of the molecular environment},
author = {M. Willenbockel and B. Stadtmüller and K. Schönauer and F. C. Bocquet and D. Lüftner and E. M. Reinisch and T. Ules and G. Koller and C. Kumpf and S. Soubatch and P. Puschnig and M. G. Ramsey and F. S. Tautz},
doi = {10.1088/1367-2630/15/3/033017},
year = {2013},
date = {2013-01-01},
journal = {New J. Phys.},
volume = {15},
pages = {033017},
abstract = {The compressed 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) herringbone monolayer structure on Ag(110) is used as a model system to investigate the role of molecule–molecule interactions at metal–organic interfaces. By means of the orbital tomography technique, we can not only distinguish the two inequivalent molecules in the unit cell but also resolve their different energy positions for the highest occupied and the lowest unoccupied molecular orbitals. Density functional theory calculations of a freestanding PTCDA layer identify the electrostatic interaction between neighboring molecules, rather than the adsorption site, as the main reason for the molecular level splitting observed experimentally.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The compressed 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) herringbone monolayer structure on Ag(110) is used as a model system to investigate the role of molecule–molecule interactions at metal–organic interfaces. By means of the orbital tomography technique, we can not only distinguish the two inequivalent molecules in the unit cell but also resolve their different energy positions for the highest occupied and the lowest unoccupied molecular orbitals. Density functional theory calculations of a freestanding PTCDA layer identify the electrostatic interaction between neighboring molecules, rather than the adsorption site, as the main reason for the molecular level splitting observed experimentally. |
2012
|
| 2. | B. Stadtmüller, M. Willenbockel, E. M. Reinisch, T. Ules, F. C. Bocquet, S. Soubatch, P. Puschnig, G. Koller, M. G. Ramsey, F. S. Tautz, C. Kumpf Orbital tomography for highly symmetric adsorbate systems Journal Article In: Europhys. Lett., vol. 100, pp. 26008, 2012. @article{Stadtmuller2012a,
title = {Orbital tomography for highly symmetric adsorbate systems},
author = {B. Stadtmüller and M. Willenbockel and E. M. Reinisch and T. Ules and F. C. Bocquet and S. Soubatch and P. Puschnig and G. Koller and M. G. Ramsey and F. S. Tautz and C. Kumpf},
doi = {10.1209/0295-5075/100/26008},
year = {2012},
date = {2012-01-01},
journal = {Europhys. Lett.},
volume = {100},
pages = {26008},
abstract = {Orbital tomography is a new and very powerful tool to analyze the angular distribution of a photoemission spectroscopy experiment. It was successfully used for organic adsorbate systems to identify (and consequently deconvolute) the contributions of specific molecular orbitals to the photoemission data. The technique was so far limited to surfaces with low symmetry like fcc(110) oriented surfaces, owing to the small number of rotational domains that occur on such surfaces. In this letter we overcome this limitation and present an orbital tomography study of a 3,4,9,10-perylene-tetra-carboxylic-dianhydride (PTCDA) monolayer film adsorbed on Ag(111). Although this system exhibits twelve differently oriented molecules, the angular resolved photoemission data still allow a meaningful analysis of the different local density of states and reveal different electronic structures for symmetrically inequivalent molecules. We also discuss the precision of the orbital tomography technique in terms of counting statistics and linear regression fitting algorithm. Our results demonstrate that orbital tomography is not limited to low-symmetry surfaces, a finding which makes a broad field of complex adsorbate systems accessible to this powerful technique.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Orbital tomography is a new and very powerful tool to analyze the angular distribution of a photoemission spectroscopy experiment. It was successfully used for organic adsorbate systems to identify (and consequently deconvolute) the contributions of specific molecular orbitals to the photoemission data. The technique was so far limited to surfaces with low symmetry like fcc(110) oriented surfaces, owing to the small number of rotational domains that occur on such surfaces. In this letter we overcome this limitation and present an orbital tomography study of a 3,4,9,10-perylene-tetra-carboxylic-dianhydride (PTCDA) monolayer film adsorbed on Ag(111). Although this system exhibits twelve differently oriented molecules, the angular resolved photoemission data still allow a meaningful analysis of the different local density of states and reveal different electronic structures for symmetrically inequivalent molecules. We also discuss the precision of the orbital tomography technique in terms of counting statistics and linear regression fitting algorithm. Our results demonstrate that orbital tomography is not limited to low-symmetry surfaces, a finding which makes a broad field of complex adsorbate systems accessible to this powerful technique. |
2011
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| 1. | P. Puschnig, E. M. Reinisch, T. Ules, G. Koller, S. Soubatch, M. Ostler, L. Romaner, F. S. Tautz, C. Ambrosch-Draxl, M. G. Ramsey Orbital tomography: Deconvoluting photoemission spectra of organic molecules Journal Article In: Phys. Rev. B, vol. 84, pp. 235427, 2011. @article{Puschnig2011,
title = {Orbital tomography: Deconvoluting photoemission spectra of organic molecules},
author = {P. Puschnig and E. M. Reinisch and T. Ules and G. Koller and S. Soubatch and M. Ostler and L. Romaner and F. S. Tautz and C. Ambrosch-Draxl and M. G. Ramsey},
doi = {10.1103/PhysRevB.84.235427},
year = {2011},
date = {2011-01-01},
journal = {Phys. Rev. B},
volume = {84},
pages = {235427},
abstract = {We study the interface of an organic monolayer with a metallic surface, i.e., PTCDA (3,4,9,10-perylene-tetracarboxylic-dianhydride) on Ag(110), by means of angle-resolved photoemission spectroscopy (ARPES) and ab initio electronic structure calculations. We present a tomographic method that uses the energy and momentum dependence of ARPES data to deconvolute spectra into individual orbital contributions beyond the limits of energy resolution. This provides an orbital-by-orbital characterization of large adsorbate systems without the need to invoke a sophisticated theory of photoemission, allowing us to directly estimate the effects of bonding on individual orbitals. Moreover, these experimental data serve as a most stringent test necessary for the further development of ab initio electronic structure theory.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
We study the interface of an organic monolayer with a metallic surface, i.e., PTCDA (3,4,9,10-perylene-tetracarboxylic-dianhydride) on Ag(110), by means of angle-resolved photoemission spectroscopy (ARPES) and ab initio electronic structure calculations. We present a tomographic method that uses the energy and momentum dependence of ARPES data to deconvolute spectra into individual orbital contributions beyond the limits of energy resolution. This provides an orbital-by-orbital characterization of large adsorbate systems without the need to invoke a sophisticated theory of photoemission, allowing us to directly estimate the effects of bonding on individual orbitals. Moreover, these experimental data serve as a most stringent test necessary for the further development of ab initio electronic structure theory. |
