Robert Carley

Structure and excitonic coupling in self-assembled monolayers of azobenzene-functionalized alkanethiols.

Optical properties and the geometric structure of self-assembled monolayers of azobenzene-functionalized alkanethiols have been investigated by UV/visible and near edge X-ray absorption fine structure spectroscopy in combination with density-functional theory. By attaching a trifluoro-methyl end group to the chromophore both the molecular tilt and twist angle of the azobenzene moiety are accessible. Based on this detailed structural analysis the energetic shifts observed in optical reflection spectroscopy can be qualitatively described within an extended dipole model. This substantiates sizable excitonic coupling among the azobenzene chromophores as an important mechanism that hinders trans to cis isomerization in densely packed self-assembled monolayers.

A high-order harmonic generation apparatus for time- and angle-resolved photoelectron spectroscopy

We present a table top setup for time- and angle-resolved photoelectron spectroscopy to investigate band structure dynamics of correlated materials driven far from equilibrium by femtosecond laser pulse excitation. With the electron-phonon equilibration time being in the order of 1-2 ps it is necessary to achieve sub-picosecond time resolution. Few techniques provide both the necessary time and energy resolution to map non-equilibrium states of the band structure. Laser-driven high-order harmonic generation is such a technique. In our experiment, a grating monochromator delivers tunable photon energies up to 40 eV. A photon energy bandwidth of 150 meV and a pulse duration of 100 fs FWHM allow us to cover the k-space necessary to map valence bands at different kz and detect outer core states.

On the electronic and geometrical structure of the trans- and cis-isomer of tetra-tert-butyl-azobenzene on Au(111)

Near edge X-ray absorption fine structure and X-ray photoelectron spectroscopy have been employed to follow the reversible trans to cis isomerization of tetra-tert-butyl-azobenzene (TBA) adsorbed on Au(111). For one monolayer the molecules adopt an adsorption geometry characteristic of the trans-TBA isomer. The azo-bridge (N = N) is aligned nearly parallel to the surface and the phenyl rings exhibit a planar orientation with a small tilt angle <or=4 degrees with respect to the surface normal. Illumination of the molecular layer at 455 nm triggers the trans to cis isomerization which is associated with a pronounced change of the geometrical and electronic structure. The N1s to pi* transition of the central azo-bridge shifts by 0.45 +/- 0.05 eV to higher photon energy and the transition dipole moment (TDM) is tilted by 59 +/- 5 degrees with respect to the surface normal. The pi-system of one phenyl ring is tilted by about 30 degrees with respect to the surface normal, while the second ring plane is oriented nearly perpendicular to the surface. This reorientation is supported by a shift and broadening of the C-H resonances associated with the tert-butyl legs of the molecule. These findings support a configuration of the photo-switched TBA molecule on Au(111) which is comparable to the cis-isomer of the free molecule. In the photo-stationary state 53 +/- 5% of the TBA molecules are switched to the cis configuration. Thermal activation induces the back reaction to trans-TBA.

Mixed self-assembled monolayers of azobenzene photoswitches with trifluoromethyl and cyano end groups

Mixed self-assembled monolayers (SAMs) of alkanethiolates carrying azobenzene chromophores with either a trifluoromethyl or a cyano substituent have been studied. High-resolution x-ray photoelectron spectroscopy proves that the ratio of adsorbed molecules can be arbitrarily adjusted via the molar fractions in solution. As a function of these molar fractions core level shifts are observed which are attributed to local work-function changes. By simulating the electric dipole field distribution, the continuous core level shifts are ascribed to a homogeneous mixture of molecules with different end groups adsorbed on adjacent lattice sites. Near-edge x-ray absorption fine structure measurements reveal formation of well-ordered SAMs. Despite the difference in dipole moment of the end groups, the molecular tilt and twist angles are identical for both single-component SAMs and a 1:1 mixed SAM.

Disparate ultrafast dynamics of itinerant and localized magnetic moments in gadolinium metal

The Heisenberg–Dirac intra-atomic exchange coupling is responsible for the formation of the atomic spin moment and thus the strongest interaction in magnetism. Therefore, it is generally assumed that intra-atomic exchange leads to a quasi-instantaneous aligning process in the magnetic moment dynamics of spins in separate, on-site atomic orbitals. Following ultrashort optical excitation of gadolinium metal, we concurrently record in photoemission the 4f magnetic linear dichroism and 5d exchange splitting. Their dynamics differ by one order of magnitude, with decay constants of 14 versus 0.8 ps, respectively. Spin dynamics simulations based on an orbital-resolved Heisenberg Hamiltonian combined with first-principles calculations explain the particular dynamics of 5d and 4f spin moments well, and corroborate that the 5d exchange splitting traces closely the 5d spin-moment dynamics. Thus gadolinium shows disparate dynamics of the localized 4f and the itinerant 5d spin moments, demonstrating a breakdown of their intra-atomic exchange alignment on a picosecond timescale.

Coverage- and Temperature-Controlled Isomerization of an Imine Derivative on Au(111)

The isomerization behavior of photochromic molecular switches is strongly influenced by adsorption on metal surfaces. For (E)-3,5-di-tert-butyl-N-(3,5-di-tert-butylbenzylidene)aniline (abbreviated as TBI for tetra-tert-butyl imine), it is found that a layer adsorbed on Au(111) can undergo an isomerization from the trans to the cis and back to the trans configuration when continuously increasing the sample temperature and accordingly decreasing the sample coverage. The conformation and adsorption geometry of TBI are determined from near-edge X-ray absorption fine structure measurements in agreement with density functional theory calculations taking into account the van der Waals interaction between adsorbate and metal surface. The coverage- and temperature-controlled conformational transitions are reversible and are driven by the higher packing density of the less stable cis-isomer in combination with the low thermal activation barrier of the trans- to cis-isomerization typical for imine derivatives. This unexpected scenario is corroborated by thermal desorption and vibrational spectroscopy as well as scanning tunneling microscopy.

The Valence Band Structure of Gadolinium Studied with Time-Resolved Photoemission

We have studied the response of the exchange split valence bands of ferromagnetic gadolinium tofemtosecond laser excitation. We observe a drop of the exchange splitting with a time constant of 0.9 ps but different response times of minority and majority spin bands. Furthermore, even above the Curie temperature there is a finite exchange splitting, which also decreases with laser excitation.

Femtosecond XUV photoelectron spectroscopy of ultrafast magnetization dynamics in gadolinium and terbium

The Lanthanide metals gadolium (Gd) and terbium (Tb) are prototypical local-moment ferromagnets. In these systems the magnetic moment derives predominantly from the partial occupancy of the localized 4f core electronic levels. Alignment of the magnetic moments between adjacent atoms in the lattice occurs by spin polarization of the itinerant 5d and 6s valence electrons in an indirect exchange (Ruderman-Kittel-Kasuya-Yosida) interaction.

Fluence-dependent dynamics of the 5d6s exchange splitting in Gd metal after femtosecond laser excitation

We investigate the fluence-dependent dynamics of the exchange-split 5d6s valence bands of Gd metal after femtosecond, near-infrared (IR) laser excitation. Time- and angle-resolved photoelectron spectroscopy (tr-ARPES) with extreme ultraviolet (XUV) probe pulses is used to simultaneously map the transient binding energies of the minority and majority spin valence bands. The decay constant of the exchange splitting increases with fluence. This reflects the slower response of the occupied majority-spin component, which we attribute to Elliot–Yafet spin-flip scattering in accordance with the microscopic three-temperature model (M3TM). In contrast, the time constant of the partly unoccupied minority-spin band stays unaffected by a change in pump fluence. Here, we introduce as an alternative to superdiffusive spin transport exchange scattering, which is an ultrafast electronic mechanism explaining the observed dynamics. Exchange scattering can reduce the spin polarization in the partially unoccupied minority-spin band and thus its energetic position without effective demagnetization.