Formation of an Organic/Metal Interface State from a Shockley Resonance

Galbraith, M. C. E.; Marks, Manuel; Tonner, Ralf; Höfer, U.

doi:10.1021/jz402249b

Cited by 41 publications

(48 citation statements)

References 36 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This value was found to be sufficiently accurate for metal-organic interfaces in the past. [48][49][50] The projection operators for the non-local part of the pseudopotentials were evaluated in real space with the exception of the linear response calculations. The Brillouin zone for the adsorption studies was sampled by a G-centred 3 Â 3 Â 1 k-point mesh generated via the Monkhorst-Pack method.…”

Section: Methodsmentioning

confidence: 99%

Molecular structure and vibrations of NTCDA monolayers on Ag(111) from density-functional theory and infrared absorption spectroscopy

Tonner

Rosenow

Jakob

2016

Phys. Chem. Chem. Phys.

Self Cite

View full text Add to dashboard Cite

The structure and vibrational properties of the metal-organic interface of 1,4,5,8-naphthalene-tetracarboxylic dianhydride (NTCDA) on Ag(111) were analysed using Fourier-transform infrared absorption spectroscopy in conjunction with density functional theory calculations including dispersion forces (PBE-D3). Mode assignments and polarizations as well as molecular distortions were determined for four adsorption geometries of NTCDA on top and bridge sites aligned either parallel or perpendicular to the Ag rows and compared to accurate calculations of the free molecule. This enables an in-depth understanding of surface effects on the computed and experimental vibrational spectra of the adsorbed NTCDA molecule. The molecule-substrate interaction comprises two major and equally important contributions: non-directional van der Waals forces between molecule and surface, and covalent bonding of the acyl oxygen atoms with underlying Ag atoms, which is quantified by charge-transfer analysis. Furthermore, adsorption energy calculations showed that the molecular axis of flat-lying NTCDA is oriented preferably in parallel to the Ag rows. The molecule is subject to particular distortions from the planar gas phase structure with covalent bonding leading to downward bending of the acyl oxygen atoms and Pauli repulsion to upward bending of the carbon core. In parallel, strong buckling of the silver surface was identified. As found in previous studies, the lowest unoccupied molecular orbital (LUMO) of the molecule slips below the Fermi level and becomes partially populated upon adsorption. Excitation of totally symmetric vibrational modes then leads to substantial interfacial dynamical charge transfer, which is convincingly reproduced in the calculated IR spectra.

show abstract

Section: Methodsmentioning

confidence: 99%

Molecular structure and vibrations of NTCDA monolayers on Ag(111) from density-functional theory and infrared absorption spectroscopy

Tonner

Rosenow

Jakob

2016

Phys. Chem. Chem. Phys.

Self Cite

View full text Add to dashboard Cite

show abstract

“…To take full advantage of this approach to quantum state engineering, it is vital to develop a detailed understanding of such moleculemetal interfaces in their native, i.e., unstructured, form. In this context, dispersive interface states which often form at these interfaces [6][7][8][9][10][11][12][13] are highly relevant because these are states that are most susceptible to the effects of lateral structuring.…”

Section: Introductionmentioning

confidence: 99%

Lateral scattering potential of the PTCDA/Ag(111) interface state

2018

View full text Add to dashboard Cite

A modified scheme of scanning tunneling spectroscopy data analysis has been used to reconstruct the band structure of a strongly dispersive two-dimensional unoccupied electronic state located at the commensurate interface between a monolayer of 3,4,9,10-perylene-tetracarboxylic dianhydride (PTCDA) and Ag(111) surface up to the fourth band in the reduced Brillouin zone of the molecular monolayer. The two-dimensional scattering potential, evaluated with the help of the measured band structure data, is highly corrugated. This shows that the accepted picture, describing the interface state of PTCDA/Ag(111) as an upshifted Shockley state of Ag(111), is incomplete. Our findings indicate that the hybridization of unoccupied molecular orbitals of PTCDA on one of the two sublattices with the metal states of Ag(111) substantially influences the interface state properties.

show abstract

“…Instead, the presence of surface/image states, or bulk states from the d‐band with a more localized character and contributing to the conduction band might be responsible, as noted in the introduction. The formation of resonance states between surface states of noble metals with organic molecules with 10 of femtosecond lifetimes are known to exist . Electrons originating from the d‐band might form resonances during the brief interaction with NO, being already more localized in character.…”

Section: Discussionmentioning

confidence: 99%

Nonadiabatic scattering of NO off Au₃ clusters: A simple and robust diabatic state manifold generation method for multiconfigurational wavefunctions

et al. 2018

View full text Add to dashboard Cite

The presence of nonadiabatic effects during the interaction of small molecules with metals has been observed experimentally for the last decades. Specially remarkable are the effects found for NO/Au, where experiments have suggested the presence of very strong vibronic coupling during the molecular scattering. However, the accurate inclusion of the nonadiabatic effects in periodic boundary conditions (PBC) theoretical methods remain an unapproachable challenge. Here, aiming to give some theoretical insight to the strong vibronic coupling, we have adopted a pragmatic point of view, taking use of an auxiliary simplified system, NO/Au3. We show the importance of nonadiabatic coupling, during the scattering of NO from a Au3 cluster, using a diabatic representation of 12 electronic states of the system, including a few charge‐transfer states. Our diabatic representation is obtained by rotating the orbital and configuration interaction (CI) vectors of a restricted active space (RAS) wavefunction. We present a strategy for extracting the best effective manifold of states relevant to the system, below some prescribed energy, directly from the RAS CI vectors. This scheme is able to disentangle a large dense manifold of adiabatic states with strong coupling and crossings. This approach is also shown to work for multireference configuration interaction (MRCI). By performing quantum propagations, we observed an increase in vibrational redistribution with increasing initial vibrational or translational energies. We suggest that these nonadiabatic effects should also be present at smaller energies in larger clusters. © 2018 Wiley Periodicals, Inc.

show abstract

Formation of an Organic/Metal Interface State from a Shockley Resonance

Cited by 41 publications

References 36 publications

Molecular structure and vibrations of NTCDA monolayers on Ag(111) from density-functional theory and infrared absorption spectroscopy

Molecular structure and vibrations of NTCDA monolayers on Ag(111) from density-functional theory and infrared absorption spectroscopy

Lateral scattering potential of the PTCDA/Ag(111) interface state

Nonadiabatic scattering of NO off Au₃ clusters: A simple and robust diabatic state manifold generation method for multiconfigurational wavefunctions

Contact Info

Product

Resources

About

Formation of an Organic/Metal Interface State from a Shockley Resonance

Cited by 41 publications

References 36 publications

Molecular structure and vibrations of NTCDA monolayers on Ag(111) from density-functional theory and infrared absorption spectroscopy

Molecular structure and vibrations of NTCDA monolayers on Ag(111) from density-functional theory and infrared absorption spectroscopy

Lateral scattering potential of the PTCDA/Ag(111) interface state

Nonadiabatic scattering of NO off Au3 clusters: A simple and robust diabatic state manifold generation method for multiconfigurational wavefunctions

Contact Info

Product

Resources

About

Nonadiabatic scattering of NO off Au₃ clusters: A simple and robust diabatic state manifold generation method for multiconfigurational wavefunctions