Tony Heinz, Postdoctoral Faculty Sponsor
Indication of non-thermal contribution to visible femtosecond laser-induced CO oxidation on Ru(0001)
JOURNAL OF CHEMICAL PHYSICS
2015; 143 (7)
We studied CO oxidation on Ru(0001) induced by 400 nm and 800 nm femtosecond laser pulses where we find a branching ratio between CO oxidation and desorption of 1:9 and 1:31, respectively, showing higher selectivity towards CO oxidation for the shorter wavelength excitation. Activation energies computed with density functional theory show discrepancies with values extracted from the experiments, indicating both a mixture between different adsorbed phases and importance of non-adiabatic effects on the effective barrier for oxidation. We simulated the reactions using kinetic modeling based on the two-temperature model of laser-induced energy transfer in the substrate combined with a friction model for the coupling to adsorbate vibrations. This model gives an overall good agreement with experiment except for the substantial difference in yield ratio between CO oxidation and desorption at 400 nm and 800 nm. However, including also the initial, non-thermal effect of electrons transiently excited into antibonding states of the O-Ru bond yielded good agreement with all experimental results.
View details for DOI 10.1063/1.4928646
View details for Web of Science ID 000360440400037
View details for PubMedID 26298142
Probing the transition state region in catalytic CO oxidation on Ru
2015; 347 (6225): 978-982
Femtosecond x-ray laser pulses are used to probe the carbon monoxide (CO) oxidation reaction on ruthenium (Ru) initiated by an optical laser pulse. On a time scale of a few hundred femtoseconds, the optical laser pulse excites motions of CO and oxygen (O) on the surface, allowing the reactants to collide, and, with a transient close to a picosecond (ps), new electronic states appear in the O K-edge x-ray absorption spectrum. Density functional theory calculations indicate that these result from changes in the adsorption site and bond formation between CO and O with a distribution of OC-O bond lengths close to the transition state (TS). After 1 ps, 10% of the CO populate the TS region, which is consistent with predictions based on a quantum oscillator model.
View details for DOI 10.1126/science.1261747
View details for Web of Science ID 000349958900034
- Electron- and phonon-coupling in femtosecond laser-induced desorption of CO from Ru(0001) SURFACE SCIENCE 2013; 615: 65–71
Real-time observation of surface bond breaking with an x-ray laser.
2013; 339 (6125): 1302-1305
We used the Linac Coherent Light Source free-electron x-ray laser to probe the electronic structure of CO molecules as their chemisorption state on Ru(0001) changes upon exciting the substrate by using a femtosecond optical laser pulse. We observed electronic structure changes that are consistent with a weakening of the CO interaction with the substrate but without notable desorption. A large fraction of the molecules (30%) was trapped in a transient precursor state that would precede desorption. We calculated the free energy of the molecule as a function of the desorption reaction coordinate using density functional theory, including van der Waals interactions. Two distinct adsorption wells-chemisorbed and precursor state separated by an entropy barrier-explain the anomalously high prefactors often observed in desorption of molecules from metals.
View details for DOI 10.1126/science.1231711
View details for PubMedID 23493709
- Catalysis in real time using X-ray lasers CHEMICAL PHYSICS LETTERS 2017; 675: 145-173
Chemical Bond Activation Observed with an X-ray Laser
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
2016; 7 (18): 3647-3651
The concept of bonding and antibonding orbitals is fundamental in chemistry. The population of those orbitals and the energetic difference between the two reflect the strength of the bonding interaction. Weakening the bond is expected to reduce this energetic splitting, but the transient character of bond-activation has so far prohibited direct experimental access. Here we apply time-resolved soft X-ray spectroscopy at a free-electron laser to directly observe the decreased bonding-antibonding splitting following bond-activation using an ultrashort optical laser pulse.
View details for DOI 10.1021/acs.jpclett.6b01543
View details for Web of Science ID 000383641800019
- Optical laser-induced CO desorption from Ru(0001) monitored with a free-electron X-ray laser: DFT prediction and X-ray confirmation of a precursor state SURFACE SCIENCE 2015; 640: 80-88
Strong Influence of Coadsorbate Interaction on CO Desorption Dynamics on Ru(0001) Probed by Ultrafast X-Ray Spectroscopy and Ab Initio Simulations
PHYSICAL REVIEW LETTERS
2015; 114 (15)
We show that coadsorbed oxygen atoms have a dramatic influence on the CO desorption dynamics from Ru(0001). In contrast to the precursor-mediated desorption mechanism on Ru(0001), the presence of surface oxygen modifies the electronic structure of Ru atoms such that CO desorption occurs predominantly via the direct pathway. This phenomenon is directly observed in an ultrafast pump-probe experiment using a soft x-ray free-electron laser to monitor the dynamic evolution of the valence electronic structure of the surface species. This is supported with the potential of mean force along the CO desorption path obtained from density-functional theory calculations. Charge density distribution and frozen-orbital analysis suggest that the oxygen-induced reduction of the Pauli repulsion, and consequent increase of the dative interaction between the CO 5σ and the charged Ru atom, is the electronic origin of the distinct desorption dynamics. Ab initio molecular dynamics simulations of CO desorption from Ru(0001) and oxygen-coadsorbed Ru(0001) provide further insights into the surface bond-breaking process.
View details for DOI 10.1103/PhysRevLett.114.156101
View details for Web of Science ID 000352990700006
View details for PubMedID 25933322
- Detection of adsorbate overlayer structural transitions using sum-frequency generation spectroscopy SURFACE SCIENCE 2015; 633: 77–81
Vacuum space charge effects in sub-picosecond soft X-ray photoemission on a molecular adsorbate layer
2015; 2 (2)
Vacuum space charge induced kinetic energy shifts of O 1s and Ru 3d core levels in femtosecond soft X-ray photoemission spectra (PES) have been studied at a free electron laser (FEL) for an oxygen layer on Ru(0001). We fully reproduced the measurements by simulating the in-vacuum expansion of the photoelectrons and demonstrate the space charge contribution of the high-order harmonics in the FEL beam. Employing the same analysis for 400 nm pump-X-ray probe PES, we can disentangle the delay dependent Ru 3d energy shifts into effects induced by space charge and by lattice heating from the femtosecond pump pulse.
View details for DOI 10.1063/1.4914892
View details for Web of Science ID 000354994100009
View details for PubMedID 26798795
View details for PubMedCentralID PMC4711610
Unique water-water coordination tailored by a metal surface
JOURNAL OF CHEMICAL PHYSICS
2013; 138 (23)
At low coverage of water on Cu(110), substrate-mediated electrostatics lead to zigzagging chains along  as observed with STM [T. Yamada, S. Tamamori, H. Okuyama, and T. Aruga, "Anisotropic water chain growth on Cu(110) observed with scanning tunneling microscopy" Phys. Rev. Lett. 96, 036105 (2006)]. Using x-ray absorption spectroscopy we find an anomalous low-energy resonance at ~533.1 eV which, based on density functional theory spectrum simulations, we assign to an unexpected configuration of water units whose uncoordinated O-H bonds directly face those of their neighbors; this interaction repeats over trough sites with enhanced electron density and is analogous to the case of a hydrated electron.
View details for DOI 10.1063/1.4809680
View details for Web of Science ID 000321012400033
View details for PubMedID 23802977
Selective Ultrafast Probing of Transient Hot Chemisorbed and Precursor States of CO on Ru(0001)
PHYSICAL REVIEW LETTERS
2013; 110 (18)
We have studied the femtosecond dynamics following optical laser excitation of CO adsorbed on a Ru surface by monitoring changes in the occupied and unoccupied electronic structure using ultrafast soft x-ray absorption and emission. We recently reported [M. Dell'Angela et al. Science 339, 1302 (2013)] a phonon-mediated transition into a weakly adsorbed precursor state occurring on a time scale of >2 ps prior to desorption. Here we focus on processes within the first picosecond after laser excitation and show that the metal-adsorbate coordination is initially increased due to hot-electron-driven vibrational excitations. This process is faster than, but occurs in parallel with, the transition into the precursor state. With resonant x-ray emission spectroscopy, we probe each of these states selectively and determine the respective transient populations depending on optical laser fluence. Ab initio molecular dynamics simulations of CO adsorbed on Ru(0001) were performed at 1500 and 3000 K providing insight into the desorption process.
View details for DOI 10.1103/PhysRevLett.110.186101
View details for Web of Science ID 000319019300011
View details for PubMedID 23683223
- Ultrafast soft X-ray emission spectroscopy of surface adsorbates using an X-ray free electron laser JOURNAL OF ELECTRON SPECTROSCOPY AND RELATED PHENOMENA 2013; 187: 9-14
- Adsorption and Cyclotrimerization Kinetics of C2H2 at a Cu(110) Surface JOURNAL OF PHYSICAL CHEMISTRY C 2012; 116 (17): 9550–60
X-ray emission spectroscopy and density functional study of CO/Fe(100)
JOURNAL OF CHEMICAL PHYSICS
2012; 136 (3)
We report x-ray emission and absorption spectroscopy studies of the electronic structure of the predissociative α(3) phase of CO bound at hollow sites of Fe(100) as well as of the on-top bound species in the high-coverage α(1) phase. The analysis is supported by density functional calculations of structures and spectra. The bonding of "lying down" CO in the hollow site is well described in terms of π to π∗ charge transfer made possible through bonding interaction also at the oxygen in the minority spin-channel. The on-top CO in the mixed, high-coverage α(1) phase is found to be tilted due to adsorbate-adsorbate interaction, but still with bonding mainly characteristic of "vertical" on-top adsorbed CO similar to other transition-metal surfaces.
View details for DOI 10.1063/1.3675834
View details for Web of Science ID 000299387700038
View details for PubMedID 22280772