Daniel Healion

Bio: Daniel Healion is an academic researcher from University of California, Irvine. The author has contributed to research in topics: Attosecond & Raman spectroscopy. The author has an hindex of 5, co-authored 7 publications receiving 97 citations.

Watching energy transfer in metalloporphyrin heterodimers using stimulated X-ray Raman spectroscopy

Abstract: Understanding the excitation energy transfer mechanism in multiporphyrin arrays is key for designing artificial light-harvesting devices and other molecular electronics applications. Simulations of the stimulated X-ray Raman spectroscopy signals of a Zn/Ni porphyrin heterodimer induced by attosecond X-ray pulses show that these signals can directly reveal electron–hole pair motions. These dynamics are visualized by a natural orbital decomposition of the valence electron wavepackets.

Simulation and visualization of attosecond stimulated x-ray Raman spectroscopy signals in trans-N-methylacetamide at the nitrogen and oxygen K-edges.

Abstract: The stimulated Raman component of the pump-probe spectrum of trans-N-methylacetamide obtained in response to two soft x-ray pulses is calculated by treating the core excitations at the Hartree–Fock static-exchange level The signal reveals the dynamics of valence-electron wave packets prepared and detected in the vicinity of a selected atom (either nitrogen or oxygen) The evolving electronic charge density as well as electronic coherence of the doorway and the window created by the two pulses are visualized using a time-dependent basis set of natural orbitals, which reveals that the wave packets consist of several entangled valence particle–hole pairs

Probing multiple core-hole interactions in the nitrogen K-edge of DNA base pairs by multidimensional attosecond X-ray spectroscopy. A simulation study.

Abstract: Two-dimensional X-ray correlation spectroscopy (2DXCS) signals of the isolated DNA bases and Watson-Crick base pairs which contain multiple absorbing nitrogen atoms are calculated. Core-hole excited states are calculated using density functional theory with the B3LYP functional and 6-311G** basis set. Sum over states calculations of the signals reveal changes in cross-peak intensities between hydrogen-bonded and stacked base pairs. Nucleobase analogues are proposed for investigating base-stacking and hydrogen-bonding interactions.

Two-dimensional x-ray correlation spectroscopy of remote core states.

Abstract: Nonlinear all-X-ray signals that involve large core-atom separation compared to the X-ray wavelengths may not be described by the dipole approximation since they contain additional phase factors Expressions for the rotationally averaged 2D X-ray photon echo signals from randomly oriented systems that take this position-dependent phase into account for arbitrary ratio between the core separation and the resonant wavelength are presented Application is made to the Se K-edge of a selenium dipeptide system

Multiple Core and Vibronic Coupling Effects in Attosecond Stimulated X-Ray Raman Spectroscopy (SXRS).

Abstract: Attosecond Stimulated X-ray Raman Spectroscopy (SXRS) is a promising technique for investigating molecular electronic structure and photochemical processes with high spatial and temporal resolution. We present a theoretical study of SXRS from multiple core excitation sites of the same element. Two issues are addressed: interference between pathways contributing the signals from different sites; and how nuclear vibrations influence the signals. Taking furan as a model system, which contains two types of carbons Cα and Cβ, we performed time-dependent density functional theory calculations and computed the SXRS signals with two pulses tuned at the carbon K-edge. Our simulations demonstrate that the SXRS signal from the Cα and Cβ sites are non-additive, owing to the significant mixed contributions (Cα 1s excitations by the pump pulse followed by Cβ 1s excitations by the probe, or vice verse). Harmonic vibrations linearly coupled to the electronic transitions are incorporated using the cumulant expansion. The nuclei act as a bath for electronic transitions which accelerate the decay of time-domain signal. The frequency-domain spectrum is modified by a small red shift and high-resolution fine-structure features are introduced.

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

Abstract: : The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Coherent methods in the X-ray sciences

Abstract: X-ray sources are developing rapidly and their coherent output is growing correspondingly. The increased coherent flux from modern X-ray sources is being matched with an associated development in experimental methods. This article reviews the literature describing the ideas that utilize the increased brilliance from modern X-ray sources. It explores how ideas in coherent X-ray science are leading to developments in other areas, and vice versa. The article describes measurements of coherence properties and uses this discussion as a base from which to describe partially coherent diffraction and X-ray phase-contrast imaging, with applications in materials science, engineering and medicine. Coherent diffraction imaging methods are reviewed along with associated experiments in materials science. Proposals for experiments to be performed with the new X-ray free-electron lasers are briefly discussed. The literature on X-ray photon-correlation spectroscopy is described and the features it has in common with other coherent X-ray methods are identified. Many of the ideas used in the coherent X-ray literature have their origins in the optical and electron communities and these connections are explored. A review of the areas in which ideas from coherent X-ray methods are contributing to methods for the neutron, electron and optical communities is presented.

Multidimensional Attosecond Resonant X-Ray Spectroscopy of Molecules: Lessons from the Optical Regime

Abstract: New free-electron laser and high-harmonic generation X-ray light sources are capable of supplying pulses short and intense enough to perform resonant nonlinear time-resolved experiments in molecules. Valence-electron motions can be triggered impulsively by core excitations and monitored with high temporal and spatial resolution. We discuss possible experiments that employ attosecond X-ray pulses to probe the quantum coherence and correlations of valence electrons and holes, rather than the charge density alone, building on the analogy with existing studies of vibrational motions using femtosecond techniques in the visible regime.

Surface-assisted dehydrogenative homocoupling of porphine molecules.

Abstract: The templated synthesis of porphyrin dimers, oligomers, and tapes has recently attracted considerable interest. Here, we introduce a clean, temperature-induced covalent dehydrogenative coupling mechanism between unsubstituted free-base porphine units yielding dimers, trimers, and larger oligomers directly on a Ag(111) support under ultrahigh-vacuum conditions. Our multitechnique approach, including scanning tunneling microscopy, near-edge X-ray absorption fine structure and photoelectron spectroscopy complemented by theoretical modeling, allows a comprehensive characterization of the resulting nanostructures and sheds light on the coupling mechanism. We identify distinct coupling motifs and report a decrease of the electronic gap and a modification of the frontier orbitals directly associated with the formation of triply fused dimeric species. This new on-surface homocoupling protocol yields covalent porphyrin nanostructures addressable with submolecular resolution and provides prospective model systems t...