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Register a new userImaging Molecular Structure through Femtosecond Photoelectron Diffraction on Aligned and Oriented Gas-Phase Molecules
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This paper gives an account of our progress towards performing femtosecond time-resolved photoelectron diffraction on gas-phase molecules in a pump-probe setup combining optical lasers and an X-ray Free-Electron Laser. We present results of two experiments aimed at measuring photoelectron angular distributions of laser-aligned 1-ethynyl-4-fluorobenzene (C8H5F) and dissociating, laseraligned 1,4-dibromobenzene (C6H4Br2) molecules and discuss them in the larger context of photoelectron diffraction on gas-phase molecules. We also show how the strong nanosecond laser pulse used for adiabatically laser-aligning the molecules influences the measured electron and ion spectra and angular distributions, and discuss how this may affect the outcome of future time-resolved photoelectron diffraction experiments.
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We report experimental results on x-ray diffraction of quantum-state-selected and strongly aligned ensembles of the prototypical asymmetric rotor molecule 2,5-diiodobenzonitrile using the Linac Coherent Light Source. The experiments demonstrate first steps toward a new approach to diffractive imaging of distinct structures of individual, isolated gas-phase molecules. We confirm several key ingredients of single molecule diffraction experiments: the abilities to detect and count individual scattered x-ray photons in single shot diffraction data, to deliver state-selected, e. g., structural-isomer-selected, ensembles of molecules to the x-ray interaction volume, and to strongly align the scattering molecules. Our approach, using ultrashort x-ray pulses, is suitable to study ultrafast dynamics of isolated molecules.
Knowledge of molecular structure is paramount in understanding, and ultimately influencing, chemical reactivity. For nearly a century, diffractive imaging has been used to identify the structures of many biologically-relevant gas-phase molecules with atomic (i.e. Angstrom, A; 1 A = 10$^{-10}$ m) spatial resolution. Unravelling the mechanisms of chemical reactions requires the capability to record multiple well-resolved snapshots of the molecular structure as it is evolving on the nuclear (i.e. femtosecond, fs; 1 fs = 10$^{-15}$ s) timescale. We present the latest, state-of-the-art ultrafast electron diffraction methods used to retrieve the molecular structure of gas-phase molecules with Angstrom and femtosecond spatio-temporal resolution. We first provide a historical and theoretical background to elastic electron scattering in its application to structural retrieval, followed by details of field-free and field-dressed ultrafast electron diffraction techniques. We discuss the application of these ultrafast methods to time-resolving chemical reactions in real-time, before providing a future outlook of the field and the challenges that exist today and in the future.
In this paper, we discuss the possibility of imaging molecular orbitals from photoelectron spectra obtained via Laser Induced Electron Diffraction (LIED) in linear molecules. This is an extension of our work published recently in Physical Review A textbf{94}, 023421 (2016) to the case of the HOMO-1 orbital of the carbon dioxide molecule. We show that such an imaging technique has the potential to image molecular orbitals at different internuclear distances in a sub-femtosecond time scale and with a resolution of a fraction of an Angstrom.
The combination of photoelectron spectroscopy and ultrafast light sources is on track to set new standards for detailed interrogation of dynamics and reactivity of molecules. A crucial prerequisite for further progress is the ability to not only detect the electron kinetic energy, as done in traditional photoelectron spectroscopy, but also the photoelectron angular distributions (PADs) in the molecular frame. Here carbonylsulfide (OCS) and benzonitrile molecules, fixed in space by combined laser and electrostatic fields, are ionized with intense, circularly polarized, 30 femtosecond laser pulses. For 1-dimensionally oriented OCS the molecular frame PADs exhibit pronounced anisotropies, perpendicular to the fixed permanent dipole moment, that are absent in PADs from randomly oriented molecules. For 3-dimensionally oriented benzonitrile additional striking structures appear due to suppression of electron emission in nodal planes of the fixed electronic orbitals. Our theoretical analysis, relying on tunneling ionization theory, shows that the PADs reflect nodal planes, permanent dipole moments and polarizabilities of both the neutral molecule and its cation. The calculated results are exponentially sensitive to changes in these molecular properties thereby pointing to exciting opportunities for time-resolved probing of valence electrons dynamics by intense circularly polarized pulses. Molecular frame PADs from oriented molecules will prove important in other contexts notably in emerging free-electron-laser studies where localized inner shell electrons are knocked off by x-ray pulses.
Ubiquitous to most molecular scattering methods is the challenge to retrieve bond distance and angle from the scattering signals since this requires convergence of pattern matching algorithms or fitting methods. This problem is typically exacerbated when imaging larger molecules or for dynamic systems with little a priori knowledge. Here, we employ laser-induced electron diffraction (LIED) which is a powerful means to determine the precise atomic configuration of an isolated gas-phase molecule with picometre spatial and attosecond temporal precision. We introduce a simple molecular retrieval method, which is based only on the identification of critical points in the oscillating molecular interference scattering signal that is extracted directly from the laboratory-frame photoelectron spectrum. The method is compared with a Fourier-based retrieval method, and we show that both methods correctly retrieve the asymmetrically stretched and bent field-dressed configuration of the asymmetric top molecule carbonyl sulfide (OCS), which is confirmed by our quantum-classical calculations.
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