Terence Mullins

Strongly aligned and oriented molecular samples at a kHz repetition rate

We demonstrate strong adiabatic laser alignment and mixed-field orientation at kHz repetition rates. We observe the degrees of alignment as large as ⟨cos2θ⟩2D=0.94 at 1 kHz operation for iodobenzene. The experimental setup consists of a kHz laser system simultaneously producing pulses of 30 fs (1.3 mJ) and 450 ps (9 mJ). A cold 1-K state-selected molecular beam is produced at the same rate by appropriate operation of an Even–Lavie valve. Quantum state selection has been obtained using an electrostatic deflector. A camera and data acquisition system records and analyses the images on a single-shot basis. The system is capable of producing, controlling (translation and rotation) and analysing cold molecular beams at kHz repetition rates and is therefore ideally suited for the recording of ultrafast dynamics in so-called ‘molecular movies’.

Alignment, Orientation, and Coulomb Explosion of Difluoroiodobenzene Studied with the Pixel Imaging Mass Spectrometry (PImMS) Camera

Laser-induced adiabatic alignment and mixed-field orientation of 2,6-difluoroiodobenzene (C6H3F2I) molecules are probed by Coulomb explosion imaging following either near-infrared strong-field ionization or extreme-ultraviolet multi-photon inner-shell ionization using free-electron laser pulses. The resulting photoelectrons and fragment ions are captured by a double-sided velocity map imaging spectrometer and projected onto two position-sensitive detectors. The ion side of the spectrometer is equipped with a pixel imaging mass spectrometry camera, a time-stamping pixelated detector that can record the hit positions and arrival times of up to four ions per pixel per acquisition cycle. Thus, the time-of-flight trace and ion momentum distributions for all fragments can be recorded simultaneously. We show that we can obtain a high degree of one-and three-dimensional alignment and mixed-field orientation and compare the Coulomb explosion process induced at both wavelengths.

Characteristic oscillations in the coherent transients of ultracold rubidium molecules using red and blue detuned pulses for photoassociation

We investigate the interaction of femtosecond laser pulses with an ensemble of ultracold rubidium atoms by applying shaped excitation pulses with two different types of spectral filtering. Although the pulses, which are frequency filtered with a high pass, have no spectral overlap with molecular states, we observe coherent molecular transients. Similar transients obtained with nearly transform-limited pulses, where only the atomic resonance is removed, reveal two differing oscillatory components. The resulting transients are compared among themselves and supported with quantum dynamical simulations which indicate a photoassociation process. The effect is due to the strong field interaction of the pulse with the colliding atom pair.

The interaction of a spectrally cut laser-pulse with a two-level atom

In this article we present a theoretical model for the light–matter interaction of a two-level atom and a femtosecond laser pulse, spectrally cut in the vicinity of the atomic resonance. The model utilizes a transformation into an interaction picture from a bare atomic state basis and is applicable to two-level systems. This transformation simplifies some of the dynamics of the interaction. A complementary intuitive picture is also presented and describes the interaction of the induced dipole with the pulses transients. The calculations are in excellent agreement with experimental measurements performed on an ultracold rubidium gas.

Time-resolved inner-shell photoelectron spectroscopy : From a bound molecule to an isolated atom

Due to its element and site specificity, inner-shell photoelectron spectroscopy is a widely used technique to probe the chemical structure of matter. Here, we show that time-resolved inner-shell photoelectron spectroscopy can be employed to observe ultrafast chemical reactions and the electronic response to the nuclear motion with high sensitivity. The ultraviolet dissociation of iodomethane (CH3I) is investigated by ionization above the iodine 4d edge, using time-resolved inner-shell photoelectron and photoion spectroscopy. The dynamics observed in the photoelectron spectra appear earlier and are faster than those seen in the iodine fragments. The experimental results are interpreted using crystal-field and spin-orbit configuration interaction calculations, and demonstrate that time-resolved inner-shell photoelectron spectroscopy is a powerful tool to directly track ultrafast structural and electronic transformations in gas-phase molecules.

High Photon Flux 70 eV HHG Source for Applications in Molecular and Solid State Physics

A 100 kHz high harmonic source with record high >1011 photons/s in single harmonics between 55-73 eV is presented. The unique capabilities are underlined by using it for coincidence experiments and measurements on magnetic samples.

Photodissociation of aligned CH3I and C6H3F2I molecules probed with time-resolved Coulomb explosion imaging by site-selective extreme ultraviolet ionization

We explore time-resolved Coulomb explosion induced by intense, extreme ultraviolet (XUV) femtosecond pulses from the FLASH free-electron laser as a method to image photo-induced molecular dynamics in two molecules, iodomethane and 2,6-difluoroiodobenzene. At an excitation wavelength of 267\,nm, the dominant reaction pathway in both molecules is neutral dissociation via cleavage of the carbon--iodine bond. This allows investigating the influence of the molecular environment on the absorption of an intense, femtosecond XUV pulse and the subsequent Coulomb explosion process. We find that the XUV probe pulse induces local inner-shell ionization of atomic iodine in dissociating iodomethane, in contrast to non-selective ionization of all photofragments in difluoroiodobenzene. The results reveal evidence of electron transfer from methyl and phenyl moieties to a multiply charged iodine ion. In addition, indications for ultrafast charge rearrangement on the phenyl radical are found, suggesting that time-resolved Coulomb explosion imaging is sensitive to the localization of charge in extended molecules.We explore time-resolved Coulomb explosion induced by intense, extreme ultraviolet (XUV) femtosecond pulses from a free-electron laser as a method to image photo-induced molecular dynamics in two molecules, iodomethane and 2,6-difluoroiodobenzene. At an excitation wavelength of 267 nm, the dominant reaction pathway in both molecules is neutral dissociation via cleavage of the carbon–iodine bond. This allows investigating the influence of the molecular environment on the absorption of an intense, femtosecond XUV pulse and the subsequent Coulomb explosion process. We find that the XUV probe pulse induces local inner-shell ionization of atomic iodine in dissociating iodomethane, in contrast to non-selective ionization of all photofragments in difluoroiodobenzene. The results reveal evidence of electron transfer from methyl and phenyl moieties to a multiply charged iodine ion. In addition, indications for ultrafast charge rearrangement on the phenyl radical are found, suggesting that time-resolved Coulomb explosion imaging is sensitive to the localization of charge in extended molecules.

Photodissociation of Aligned

We explore time-resolved Coulomb explosion induced by intense, extreme ultraviolet (XUV) femtosecond pulses from the FLASH free-electron laser as a method to image photo-induced molecular dynamics in two molecules, iodomethane and 2,6-difluoroiodobenzene. At an excitation wavelength of 267\,nm, the dominant reaction pathway in both molecules is neutral dissociation via cleavage of the carbon--iodine bond. This allows investigating the influence of the molecular environment on the absorption of an intense, femtosecond XUV pulse and the subsequent Coulomb explosion process. We find that the XUV probe pulse induces local inner-shell ionization of atomic iodine in dissociating iodomethane, in contrast to non-selective ionization of all photofragments in difluoroiodobenzene. The results reveal evidence of electron transfer from methyl and phenyl moieties to a multiply charged iodine ion. In addition, indications for ultrafast charge rearrangement on the phenyl radical are found, suggesting that time-resolved Coulomb explosion imaging is sensitive to the localization of charge in extended molecules.We explore time-resolved Coulomb explosion induced by intense, extreme ultraviolet (XUV) femtosecond pulses from a free-electron laser as a method to image photo-induced molecular dynamics in two molecules, iodomethane and 2,6-difluoroiodobenzene. At an excitation wavelength of 267 nm, the dominant reaction pathway in both molecules is neutral dissociation via cleavage of the carbon–iodine bond. This allows investigating the influence of the molecular environment on the absorption of an intense, femtosecond XUV pulse and the subsequent Coulomb explosion process. We find that the XUV probe pulse induces local inner-shell ionization of atomic iodine in dissociating iodomethane, in contrast to non-selective ionization of all photofragments in difluoroiodobenzene. The results reveal evidence of electron transfer from methyl and phenyl moieties to a multiply charged iodine ion. In addition, indications for ultrafast charge rearrangement on the phenyl radical are found, suggesting that time-resolved Coulomb explosion imaging is sensitive to the localization of charge in extended molecules.

\mathrm{CH_3I}

One of the ultimate goals of molecular physics is the possibility of accessing the structural dynamics of molecules through external fields. To this end, one first has to image the molecular structure and dynamics with few-fs temporal resolution and atomic spatial resolution simultaneously. Laser induced electron diffraction (LIED) is a very promising candidate for the spatiotemporal imaging of small molecules [1]. So far most of the LIED experiments have been performed on isotropic molecular samples [2, 3]. Recently, this technique was used to derive C-C and C-H bond lengths of acetylene from a molecular-frame measurement [4]. Here, we present the investigation of the geometry of strongly aligned OCS molecules by using IR-driven laser induced electron diffraction.

and

Molecules in the gas-phase can be treated as isolated systems without influence from the environment. Gaining further control over the molecules, such as quantum state or conformer selection, or/and fixing the molecular axis in space, can be highly advantageous or simply necessary for a variety of experiments aiming at, for instance, probing of the molecular structure, or molecular frame dependent properties such as molecular-frame photo angular distributions.