arXiv subjects

Gerard Meijer

Publications and source records attributed to Gerard Meijer.

At least 37 records · Page 2Linked to original sources

arXiv2022

Spectroscopic characterization of singlet-triplet doorway states of aluminum monofluoride

Aluminum monofluoride (AlF) possesses highly favorable properties for laser cooling, both via the A$^1Π$ and a$^3Π$ states. Determining efficient pathways between the singlet and the triplet manifold of electronic states will be advantageous for future experiments at ultralow temperatures. The lowest rotational levels of the A$^1Π, v=6$ and b$^3Σ^+, v=5$ states of AlF are nearly iso-energetic and interact via spin-orbit coupling. These levels thus have a strongly mixed spin-character and provide a singlet-triplet doorway. We here present a hyperfine resolved spectroscopic study of the A$^1Π, v=6$ // b$^3Σ^+, v=5$ perturbed system in a jet-cooled, pulsed molecular beam. From a fit to the observed energies of the hyperfine levels, the fine and hyperfine structure parameters of the coupled states, their relative energies as well as the spin-orbit interaction parameter are determined. The standard deviation of the fit is about 15 MHz. We experimentally determine the radiative lifetimes of selected hyperfine levels by time-delayed ionization, Lamb dip spectroscopy and accurate measurements of the transition lineshapes. The measured lifetimes range between 2 ns and 200 ns, determined by the degree of singlet-triplet mixing for each level.

quant-ph↗

arXiv2022

Imaging of chemical kinetics at the water-water interface in a free-flowing liquid flat-jet

We present chemical kinetics measurements of the luminol oxydation chemiluminescence reaction at the interface between two aqueous solutions, using liquid jet technology. Free-flowing iquid microjets are a relatively recent development that has found its way into a growing number of applications in spectroscopy and dynamics. A variant thereof, called flat-jet, is obtained when two cylindrical jets of a liquid are crossed, leading to a chain of planar leaf-shaped structures of the flowing liquid. We here show that in the first leaf of this chain the fluids do not exhibit turbulent mixing, providing a clean interface between the liquids from the impinging jets. We also show, using the example of the luminol chemiluminescence reaction, how this setup can be used to obtain kinetics information from friction-less flow and by circumventing the requirement for rapid mixing but by intentionally suppressing all turbulent mixing and instead relying on diffusion.

physics.chem-ph↗

arXiv2021

A setup for studies of photoelectron circular dichroism from chiral molecules in aqueous solution

We present a unique experimental design that enables the measurement of photoelectron circular dichroism (PECD) from chiral molecules in aqueous solution. The effect is revealed from the intensity difference of photoelectron emission into a backward-scattering angle relative to the photon propagation direction when ionizing with circularly polarized light of different helicity. This leads to asymmetries (normalized intensity differences) that depend on the handedness of the chiral sample and exceed the ones in conventional dichroic mechanisms by orders of magnitude. The asymmetry is largest for photon energies within several electron volts above the ionization threshold. A primary aim is to explore the effect of hydration on PECD. The modular and flexible design of our experimental setup EASI (Electronic structure from Aqueous Solutions and Interfaces) also allows for detection of more common photoelectron angular distributions (PADs), requiring distinctively different detection geometries, and typically using linearly polarized light. A microjet is used for liquid-sample delivery. We describe EASI's technical features and present two selected experimental results, one based on synchrotron-light measurements and the other performed in the laboratory, using monochromatized He-II $α$ radiation. The former demonstrates the principal effectiveness of PECD detection, illustrated for prototypic gas-phase fenchone. We also discuss the first data from liquid fenchone. In the second example we present valence photoelectron spectra from liquid water and NaI aqueous solution, here obtained from a planar-surface microjet (flatjet). This new development features a more favorable symmetry for angle-dependent photoelectron measurements.

physics.chem-ph↗

arXiv2021

Dynamics of translational and rotational thermalization of AlF molecules via collisions with cryogenic helium

We investigated helium-mediated translational and rotational thermalization of the aluminum monofluoride (AlF) molecule at cryogenic temperatures via a new $ab \ initio$ potential energy surface (PES) and quantum multichannel scattering theory. Our examination of the elastic and rotationally inelastic channels revealed that helium is an efficient quencher of AlF at temperatures relevant to buffer gas cooling experiments ($\sim1$ mK to $10$ K). We also showed that this conclusion is robust against possible inaccuracies of the PES.

physics.chem-ph↗

arXiv2021

A New Design for a Traveling-Wave Zeeman Decelerator: I. Theory

The concept of a novel traveling wave Zeeman deccelerator based on a double-helix wire geometry capable of decelerating paramagnetic species with high efficiency is presented. A moving magnetic trap is created by running time-dependent currents through the decelerator coils. Paramagnetic species in low-field-seeking Zeeman states are confined in the moving traps and transported to the end of the decelerator with programmable velocities. Here, we present the theoretical foundations underlying the working principle of the traveling-trap decelerator. Using trajectory simulations, we characterise the performance of the new device and explore the conditions for phase-space stability of the transported molecules.

physics.chem-ph↗

arXiv2021

A New Design for a Traveling-Wave Zeeman Decelerator: II. Experiment

A novel traveling-wave Zeeman decelerator based on a double-helix coil geometry capable of decelerating paramagnetic molecules with high efficiency is presented. Moving magnetic traps are generated by applying time-dependent currents through the decelerator coils. Paramagnetic molecules in low-field-seeking Zeeman states are confined inside the moving traps which are decelerated to lower forward velocities. As a prototypical example, we demonstrate the deceleration of OH radicals from an initial velocity of 445 m/s down to various final velocities. The experimental results are analyzed and numerically reproduced with the help of trajectory simulations confirming the phase-space stability and efficiency of the deceleration of the molecules in the new device.

physics.chem-ph↗

arXiv2021

Accurate Vertical Ionization Energy and Work Function Determinations of Liquid Water and Aqueous Solutions

The absolute-scale electronic energetics of liquid water and aqueous solutions, both in the bulk and at associated interfaces, are the central determiners of water-based chemistry. However, such information is generally experimentally inaccessible. We demonstrate that a refined implementation of the liquid microjet photoelectron spectroscopy (PES) technique can be adopted to address this. Implementing concepts from condensed matter physics, we establish novel all-liquid-phase vacuum and equilibrated solution-metal-electrode Fermi level referencing procedures. This enables the precise and accurate quantification of previously elusive solute-induced perturbations of water's electronic energetics and vertical ionization energy (VIE) definition on an absolute and universal chemical potential scale. Applying these procedures over a broad range of ionization energies, we accurately and respectively determine the VIE and oxidative stability of liquid water as 11.33 $\pm$ 0.02 eV and 6.60 $\pm$ 0.08 eV with respect to its liquid-vacuum-interface potential and Fermi level. Combining our referencing schemes, we determine the work function of liquid water as 4.73 $\pm$ 0.09 eV. Further, applying our novel approach to a pair of exemplary aqueous solutions, we extract absolute VIEs of aqueous iodide anions, reaffirm the robustness of water's electronic structure to high bulk salt concentrations, and quantify reference-level dependent reductions of water's VIE and a 0.48 $\pm$ 0.13 eV contraction of the solution's work function upon partial hydration of a known surfactant. Our combined experimental accomplishments mark a major advance in our ability to quantify electronic-structure interactions and chemical reactivity in water, which now explicitly extends to the measurement of absolute-scale bulk and interfacial solution energetics, including those of relevance to aqueous electrochemical processes.

physics.chem-ph↗

arXiv2021

Optical cycling of AlF molecules

Aluminium monofluoride (AlF) is a promising candidate for laser cooling and trapping at high densities. We show efficient production of AlF in a bright, pulsed cryogenic buffer gas beam, and demonstrate rapid optical cycling on the Q rotational lines of the $A^1Π\leftrightarrow X^1Σ^+ $ transition. We measure the brightness of the molecular beam to be $>10^{12}$ molecules per steradian per pulse in a single rotational state and present a new method to determine its velocity distribution in a single shot. The photon scattering rate of the optical cycling scheme is measured using three different methods, and is compared to theoretical predictions of the optical Bloch equations and a simplified rate equation model. Despite the large number of Zeeman sublevels (up to 216 for the Q(4) transition) involved, a high scattering rate of at least $17(2)\times 10^6$ s$^{-1}$ can be sustained using a single, fixed-frequency laser without the need to modulate the polarisation. We deflect the molecular beam using the radiation pressure force and measure an acceleration of $8.7(1.5)\times 10^5$ m/s$^2$. We demonstrate that losses from the optical cycle due to vibrational branching to $X^1Σ^+, v''=1$ can be addressed efficiently with a single repump laser. Further, we investigate two other loss channels, parity mixing by stray electric fields and photo-ionisation. The upper bounds for these effects are sufficiently low to allow loading into a magneto optical trap.

physics.atom-ph↗

arXiv2021

Low-energy constraints on photoelectron spectra measured from liquid water and aqueous solutions

We report on the effects of electron collision and indirect ionization processes, occurring at photoexcitation and electron kinetic energies well below 30 eV on the photoemission spectra of liquid water. We show that the nascent photoelectron spectrum and, hence, the inferred electron binding energy can only be accurately determined if electron energies are large enough that cross sections for quasi-elastic scattering processes, such as vibrational excitation, are negligible. Otherwise, quasi-elastic scattering leads to strong, down-to-few-meV kinetic energy scattering losses from the direct photoelectron features, which manifest in severely distorted intrinsic photoelectron peak shapes. The associated cross-over point from predominant (known) electronically inelastic to quasi-elastic scattering seems to arise at surprisingly large electron kinetic energies, of approximately 10-14 eV. Concomitantly, we present evidence for the onset of indirect, autoionization phenomena (occurring via superexcited states) within a few eV of the primary and secondary ionization thresholds. These processes are inferred to compete with the direct ionization channels and primarily produce low-energy photoelectrons at photon and electron impact excitation energies below ~15 eV. Our results highlight that vibrational inelastic electron scattering processes and neutral photoexcitation and autoionization channels become increasingly important when photon and electron kinetic energies are decreased towards the ionization threshold. Correspondingly, we show that for neat water and aqueous solutions, great care must be taken when quantitatively analyzing photoelectron spectra measured too close to the ionization threshold. Such care is essential for both the accurate determination of solvent and solute ionization energies as well as photoelectron branching ratios and peak magnitudes.

physics.chem-ph↗

arXiv2020

Characterisation of the $b^3Σ^+, v=0$ State and Its Interaction with the $A^1Π$ State in Aluminium Monofluoride

Recently, we determined the detailed energy level structure of the $X^1Σ^+$, $A^1Π$ and $a^3Π$ states of AlF that are relevant to laser cooling and trapping experiments. Here, we investigate the $b^3Σ^+, v=0$ state of the AlF molecule. A rotationally-resolved (1+2)-REMPI spectrum of the $b^3Σ^+, v'=0 \leftarrow a^3Π, v''=0$ band is presented and the lifetime of the $b^3Σ^+, v=0$ state is measured to be 190(2)~ns. Hyperfine-resolved, laser-induced fluorescence spectra of the $b^3Σ^+, v'=0 \leftarrow X^1Σ^+, v''=1$ and the $b^3Σ^+, v'=0 \leftarrow a^3Π, v''=0$ bands are recorded to determine fine- and hyperfine structure parameters. The interaction between the $b^3Σ^+, v=0$ and the nearby $A^1Π$ state is studied and the magnitude of the spin-orbit coupling between the two electronic states is derived using three independent methods to give a consistent value of 10(1)~cm$^{-1}$. The triplet character of the $A$ state causes an $A\rightarrow a$ loss from the main $A-X$ laser cooling cycle below the 10$^{-6}$ level.

physics.atom-ph↗

arXiv2020

A data-driven approach to determine dipole moments of diatomic molecules

We present a data-driven approach for the prediction of the electric dipole moment of diatomic molecules, which is one of the most relevant molecular properties. In particular, we apply Gaussian process regression to a novel dataset to show that dipole moments of diatomic molecules can be learned, and hence predicted, with a relative error <5%. The dataset contains the dipole moment of 162 diatomic molecules, the most exhaustive and unbiased dataset of dipole moments up to date. Our findings show that the dipole moment of diatomic molecules depends on atomic properties of the constituents atoms: electron affinity and ionization potential, as well as on (a feature related to) the first derivative of the electronic kinetic energy at the equilibrium distance.

physics.chem-ph↗

arXiv2020

On the universality of spectroscopic constants of diatomic molecules

We show, through a machine learning approach, that the equilibrium distance, harmonic vibrational frequency, and binding energy of diatomic molecules are universally related. In particular, the relationships between spectroscopic constants are valid independently of the molecular bond. However, they depend strongly on the group and period of the constituent atoms. As a result, we show that by employing the group and period of atoms within a molecule, the spectroscopic constants are predicted with an accuracy of $\lesssim 5\%$. Finally, the same universal relationships are satisfied when spectroscopic constants from {\it ab initio} and density functional theory (DFT) electronic structure methods are employed.

physics.chem-ph↗

arXiv2019

On the $Λ$-doubling in the B$^3Π_1$ state of TlF

Thallium monofluoride (TlF) is a prime candidate molecule for precision measurements aimed at discovering new physics. Optical cycling on the B $\leftarrow$ X transition around 271 nm enhances this potential. Hyperfine resolved ultraviolet spectra have been reported to determine the degree of rotational level mixing in the B-state and the efficiency of laser cooling on the B $\leftarrow$ X transition [E. B. Norrgard ${\it et~al.}$, Physical Review A ${\bf 95}$, 062506 (2017)]. Using these high-resolution spectra, the hyperfine structure in the B-state of TlF is re-analysed and the magnitude of the $Λ$-doubling in the B-state is discussed.

physics.chem-ph↗

arXiv2015

Advanced switching schemes in a Stark decelerator

We revisit the operation of the Stark decelerator and present a new, optimized operation scheme, which substantially improves the efficiency of the decelerator at both low and high final velocities, relevant for trapping experiments and collision experiments, respectively. Both experimental and simulation results show that this new mode of operation outperforms the schemes which have hitherto been in use. This new mode of operation could potentially be extended to other deceleration techniques.

physics.chem-ph↗

arXiv2014

Measuring and manipulating the temperature of cold molecules trapped on a chip

We demonstrate the measurement and manipulation of the temperature of cold CO molecules in a microchip environment. Through the use of time-resolved spatial imaging, we are able to observe the phase-space distribution of the molecules, and hence deduce the corresponding temperature. We do this both by observing the expansion of the molecular ensemble in time and through the use of numerical trajectory simulations. Furthermore, we demonstrate the adiabatic cooling of the trapped molecular sample and discuss this process.

physics.atom-ph↗

arXiv2014

X-ray diffraction from isolated and strongly aligned gas-phase molecules with a free-electron laser

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.

physics.atom-ph↗

arXiv2013

Stark deceleration of NO radicals

We report on the Stark deceleration of a pulsed molecular beam of NO radicals. Stark deceleration of this chemically important species has long been considered unfeasible due to its small electric dipole moment of 0.16 D. We prepared the NO radicals in the X 2Π3/2, v=0, J=3/2 spin-orbit excited state from the X 2Π1/2, v=0, J=1/2 ground state by Franck-Condon pumping via the A 2Σ+ state. The larger effective dipole moment in the J=3/2 level of the X 2Π3/2, v=0 state, in combination with a 316-stages-long Stark decelerator, allowed us to decelerate NO radicals from 315.0 m/s to 229.2 m/s, thus removing 47 % of their kinetic energy. The measured time-of-flight profiles of the NO radicals exiting the decelerator show good agreement with the outcome of numerical trajectory simulations.

physics.chem-ph↗

arXiv2012

Scattering resonances in slow NH${}_3$-He collisions

We theoretically study slow collisions of NH$_3$ molecules with He atoms, where we focus in particular on the observation of scattering resonances. We calculate state-to-state integral and differential cross sections for collision energies ranging from 10${}^{-4}$ cm$^{-1}$ to 130 cm$^{-1}$, using fully converged quantum close-coupling calculations. To describe the interaction between the NH${}_3$ molecules and the He atoms, we present a four-dimensional potential energy surface, based on an accurate fit of 4180 {\it ab initio} points. Prior to collision, we consider the ammonia molecules to be in their antisymmetric umbrella state with angular momentum $j=1$ and projection $k=1$, which is a suitable state for Stark deceleration. We find pronounced shape and Feshbach resonances, especially for inelastic collisions into the symmetric umbrella state with $j=k=1$. We analyze the observed resonant structures in detail by looking at scattering wavefunctions, phase shifts, and lifetimes. Finally, we discuss the prospects for observing the predicted scattering resonances in future crossed molecular beam experiments with a Stark-decelerated NH$_3$ beam.

physics.chem-ph↗