Core excitations of naphthalene: Vibrational structure versus chemical shifts

Minkov, I. M.; Gel’mukhanov, Faris; Friedlein, Rainer; Osikowicz, Wojciech; Suess, C.; Öhrwall, Gunnar; Sorensen, S. L.; Braun, Slawomir; Murdey, Richard; Salaneck, W. R.; Ågren, Hans

doi:10.1063/1.1784450

Cited by 45 publications

(66 citation statements)

References 31 publications

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“…The asymmetric low-energy peak in the X-ray absorption spectrum in Fig. 7 at around 285 eV is attributed to excitations from the naphthalene C 1s levels to the LUMO [27], while the higher energy peak at around 288 eV stems primarily from excitations C 1s X-ray absorption spectra for the same non-annealed submonolayer NDCA/Ag(110) preparation as in Fig. 6(b).…”

Section: Xas Resultsmentioning

confidence: 90%

“…An intensity offset was applied to the spectra for reasons of presentation. The incidence angle was measured from the surface normal of electrons from the carboxylic C 1s level into the LUMO [28] plus a possible admixture of further excitations on the naphthalene part of the molecule [27]. The main part of the intensity at higher energies is attributed to the excitation of a σ * resonance.…”

Section: Xas Resultsmentioning

confidence: 99%

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Interplay of adsorbate-adsorbate and adsorbate-substrate interactions in self-assembled molecular surface nanostructures

Schnadt

Vang

et al. 2010

Nano Res.

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The adsorption of 2,6-naphthalenedicarboxylic acid (NDCA) molecules on the Ag(110), Cu(110), and Ag(111) surfaces at room temperature has been studied by means of scanning tunnelling microscopy (STM). Further supporting results were obtained using X-ray photoelectron spectroscopy (XPS) and soft X-ray absorption spectroscopy (XAS). On the Ag(110) support, which had an average terrace width of only 15 nm, the NDCA molecules form extended one-dimensional (1-D) assemblies, which are oriented perpendicular to the step edges and have lengths of several hundred nanometres. This shows that the assemblies have a large tolerance to monatomic surface steps on the Ag(110) surface. The observed behaviour is explained in terms of strong intermolecular hydrogen bonding and a strong surface-mediated directionality, assisted by a sufficient degree of molecular backbone flexibility. In contrast, the same kind of step-edge crossing is not observed when the molecules are adsorbed on the isotropic Ag(111) or more reactive Cu(110) surfaces. On Ag(111), similar 1-D assemblies are formed to those on Ag(110), but they are oriented along the step edges. On Cu(110), the carboxylic groups of NDCA are deprotonated and form covalent bonds to the surface, a situation which is also achieved on Ag(110) by annealing to 200 °C . These results show that the formation of particular self-assembled molecular nanostructures depends significantly on a subtle balance between the adsorbate-adsorbate and adsorbate-substrate interactions and that kinetic factors play an important role.

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Section: Xas Resultsmentioning

confidence: 90%

Section: Xas Resultsmentioning

confidence: 99%

Interplay of adsorbate-adsorbate and adsorbate-substrate interactions in self-assembled molecular surface nanostructures

Schnadt

Vang

et al. 2010

Nano Res.

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“…[31,42] However, vibrational structure has been observed in the near-edge xray absorption fine structure (NEXAFS) spectra of large molecules, including naphthalene. [32] Given the measured and calculated linewidths of the core electronic transitions and the frequencies of the vibrations in aromatic molecules like benzene and naphthalene as well as observation of vibrational structure in NEXAFS spectra, it is likely that quantum mechanical interference plays a significant role in determining the spectra observed in RIXS experiments of these systems.…”

Section: Spontaneous Inelastic Scattering Of Lg Beams From Vibromentioning

confidence: 99%

“…A model of this form has been used to explain coupling between resonant core electronic transitions and both totally and non-totally symmetric vibrations, such as those examined below. [31,32] For this treatment of resonant inelastic light scattering, we assume the interaction operator, V , derived in the previous section can only connect vibronic states on different electronic manifolds. Using Fig.…”

Section: B Model Vibronic Moleculementioning

confidence: 99%

Examining resonant inelastic spontaneous scattering of classical Laguerre-Gauss beams from molecules

Rury

2013

Phys. Rev. A

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This paper theoretically treats the spontaneous resonant inelastic scattering of Laguerre-Gauss (LG) beams from the totally symmetric vibrations of complex polyatomic molecules within the semiclassical framework. We develop an interaction Hamiltonian that accounts for the position of the molecule within the excitation beam to derive the effective differential scattering cross-section of a classical LG beam from a molecule using the frequency domain third order nonlinear optical response function. To gain physical insight into this scattering process, we utilize a model vibronic molecule to study the changes to this scattering process. For specific molecular parameters including vibrational frequency and relative displacement of the involved electronic states, this investigation shows that an incident LG beam asymmetrically enhances one of two participating excitation transitions causing modulation of the interference present in the scattering process. This modulation allows a pathway to coherent control of resonant inelastic scattering from complex, poly-atomic molecules. We discuss the possible application of this control to the resonant x-ray inelastic scattering (RIXS) of small poly-atomic molecules central to applications ranging from single molecule electronics to solar energy science.

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“…More detailed approaches calculate Franck-Condon factors based on a vibrational eigenmode analysis in the ground and excited states. These factors are used to modulate a single electronic transition and help to reproduce asymmetric lineshapes associated with accompanying transitions to excited vibrational modes [9,22,23]. However, the Franck-Condon approximation ignores the impact of nuclear motion on the electronic transition amplitude.…”

Section: Pacs Numbers: Unknownmentioning

confidence: 99%

Effects of vibrational motion on core-level spectra of prototype organic molecules

Uejio

Schwartz

Saykally

2008

Chemical Physics Letters

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A computational approach is presented for prediction and interpretation of core-level spectra of complex molecules. Applications are presented for several isolated organic molecules, sampling a range of chemical bonding and structural motifs. Comparison with gas phase measurements indicate that spectral lineshapes are accurately reproduced both above and below the ionization potential, without resort to ad hoc broadening. Agreement with experiment is significantly improved upon inclusion of vibrations via molecular dynamics sampling. We isolate and characterize spectral features due to particular electronic transitions enabled by vibrations, noting that even zero-point motion is sufficient in some cases. PACS numbers: UnknownWhen applied to molecular systems, core level spectroscopies are powerful probes of both occupied and unoccupied electronic states, uniquely revealing intimate details of both intra-and inter-molecular interactions [1]. Methods involving x-ray absorption (XAS, NEXAFS, XANES) or x-ray photo-electron spectroscopy (XPS) are increasingly being applied to complex molecular systems, including nucleotides, peptides and large organic molecules [2]. However, a major limitation of this technology is the fact that extraction of molecular information from these experiments often depends explicitly on comparisons with theoretical calculations, which are extremely challenging to perform at experimental accuracy. In this Letter, we describe the extension of a recently developed method for predicting core-level spectra of condensed phases [3] to isolated organic molecules -pyrrole, s-triazine, pyrrolidine and glycine -which demonstrates qualitative improvements over existing methods [4][5][6] in comparison with experiment and provides new insights into the origins of particular spectral features in terms of coupling of electronic and vibrational degrees of freedom.The challenges for simulating gas phase core-level spectra are maintaining accuracy in the following areas: (1) description of the core-hole excited state; (2) representation of both bound excitonic states below the ionization potential (IP) and resonance states in the continuum above the IP; and (3) inclusion of vibrational effects, either due to experiments being performed near room temperature, or from intrinsic zero-point motion.Density functional theory (DFT) [7,8] has proved accurate in reproducing the excitation energies associated with core-level spectra via total energy differences (socalled ∆SCF or ∆KS) [9]. Accordingly, we model the lowest energy core-level excited state self-consistently using a full core-hole and excited electron (XCH) [3]. This is particularly important for molecular systems, where screening of the core-hole excitation is greatly enhanced by the presence of the excited electron, which can be strongly bound to the core-hole in the lowest energy excited state. In contrast, for non-molecular condensed phases, such as covalent and ionic crystalline solids, the inherent dielectric screening of the valence charge density o...

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Core excitations of naphthalene: Vibrational structure versus chemical shifts

Cited by 45 publications

References 31 publications

Interplay of adsorbate-adsorbate and adsorbate-substrate interactions in self-assembled molecular surface nanostructures

Interplay of adsorbate-adsorbate and adsorbate-substrate interactions in self-assembled molecular surface nanostructures

Examining resonant inelastic spontaneous scattering of classical Laguerre-Gauss beams from molecules

Effects of vibrational motion on core-level spectra of prototype organic molecules

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