Time-dependent Wavepackets and Photoionization – CS2

Time-dependent Wavepackets and Photoionization – CS2

Our ongoing work on the calculation of time-dependent wavepackets and observables in photoionization is now collected in an OSF project (DOI: 10.17605/OSF.IO/RJMPD). Aspects of this work have previously been published, but much of the detail and methodology underlying the calculations has remained sitting on our computers. As part of our Open Science Initiative, we’re letting this data go free! Head over to the OSF project “Time-dependent Wavepackets and Photoionization – CS2” for more.

Figure shows TRPADs results (a) Calculated TRPADs (0.7eV) (b), (c) Comparison with expt. TRPADs (discrete times).

Press Release: The Inner Lives of Molecules

Press Release: The Inner Lives of Molecules

Our latest work with the PImMS camera, femtosecond VUV pulses, and velocity-map imaging, has been picked up for a press release by AIP.

The Inner Lives of Molecules

New method takes 3-D images of molecules in action

WASHINGTON, D.C., April 4, 2017 — Quantum mechanics rules. It dictates how particles and forces interact, and thus how atoms and molecules work — for example, what happens when a molecule goes from a higher-energy state to a lower-energy one. But beyond the simplest molecules, the details become very complex.

“Quantum mechanics describes how all this stuff works,” said Paul Hockett of the National Research Council of Canada. “But as soon as you go beyond the two-body problem, you can’t solve the equations.” So, physicists must rely on computer simulations and experiments.

Now, he and an international team of researchers from Canada, the U.K. and Germany have developed a new experimental technique to take 3-D images of molecules in action. This tool, he said, can help scientists better understand the quantum mechanics underlying bigger and more complex molecules.

The new method, described in The Journal of Chemical Physics, from AIP Publishing, combines two technologies. The first is a camera developed at Oxford University, called the Pixel-Imaging Mass Spectrometry (PImMS) camera. The second is a femtosecond vacuum ultraviolet light source built at the NRC femtolabs in Ottawa.

Mass spectrometry is a method used to identify unknown compounds and to probe the structure of molecules. In most types of mass spectrometry, a molecule is fragmented into atoms and smaller molecules that are then separated by molecular weight. In time-of-flight mass spectrometry, for example, an electric field accelerates the fragmented molecule. The speed of those fragments depends on their mass and charge, so to weigh them, you measure how long it takes for them to hit the detector.

Most conventional imaging detectors, however, can’t discern exactly when one particular particle hits. To measure timing, researchers must use methods that effectively act as shutters, which let particles through over a short time period. Knowing when the shutter is open gives the time-of-flight information. But this method can only measure particles of the same mass, corresponding to the short time the shutter is open.

The PImMS camera, on the other hand, can measure particles of multiple masses all at once. Each pixel of the camera’s detector can time when a particle strikes it. That timing information produces a three-dimensional map of the particles’ velocities, providing a detailed 3-D image of the fragmentation pattern of the molecule.

To probe molecules, the researchers used this camera with a femtosecond vacuum ultraviolet laser. A laser pulse excites the molecule into a higher-energy state, and just as the molecule starts its quantum mechanical evolution — after a few dozen femtoseconds –another pulse is fired. The molecule absorbs a single photon, a process that causes it to fall apart. The PImMS camera then snaps a 3-D picture of the molecular debris.

By firing a laser pulse at later and later times at excited molecules, the researchers can use the PImMS camera to take snapshots of molecules at various stages while they fall into lower energy states. The result is a series of 3-D blow-by-blow images of a molecule changing states.

The researchers tested their approach on a molecule called C2F3I. Although a relatively small molecule, it fragmented into five different products in their experiments. The data and analysis software is available online as part of an open science initiative, and although the results are preliminary, Hockett said, the experiments demonstrate the power of this technique.

“It’s effectively an enabling technology to actually do these types of experiments at all,” Hockett said. It only takes a few hours to collect the kind of data that would take a few days using conventional methods, allowing for experiments with larger molecules that were previously impossible.

Then researchers can better answer questions like: How does quantum mechanics work in larger, more complex systems? How do excited molecules behave and how do they evolve?

“People have been trying to understand these things since the 1920s,” Hockett said. “It’s still a very open field of investigation, research, and debate because molecules are really complicated. We have to keep trying to understand them.”

Text reproduced from AIP.

The article, Time-resolved multi-mass ion imaging: femtosecond UV-VUV pump-probe spectroscopy with the PImMS camera, is now published in the Journal of Chemical Physics, and also available via the arXiv 1702.00744 and Authorea (original text), DOI: 10.22541/au.149030711.19068540.

The full dataset and analysis scripts are available via OSF, DOI: 10.17605/OSF.IO/RRFK3.

Angle-resolved RABBIT: new work and presentation

Angle-resolved RABBIT: new work and presentation

The above image shows simulated velocity map images (left, middle) and angle and time-resolved measurements (right) for angle-resolved RABBIT measurements. In this type of measurement, XUV and IR pulses are combined, and create a set of 1 and 2-photon bands in the photoelectron spectrum. The presence of multiple interfering pathways to each final photoelectron band (energy) results in complex and information rich interferograms, with both angle and time-dependence.

A manuscript detailing this work is currently in preparation, and a recent presentation detailing some aspects of the work can be found on Figshare.

Update 24th March – new manuscript, Angle-resolved RABBIT: theory and numerics, pre-print available.

Monitoring Non-adiabatic Dynamics in CS2 with Time- and Energy-Resolved Photoelectron Spectra of Wavepackets

Monitoring Non-adiabatic Dynamics in CS2 with Time- and Energy-Resolved Photoelectron Spectra of Wavepackets

Feb. 2017 – New article in Chemical Physics Letters:

Monitoring Non-adiabatic Dynamics in CS2 with Time- and Energy-Resolved Photoelectron Spectra of Wavepackets

Kwanghsi Wang(a) Vincent McKoy(a)Paul Hockett(b)Albert Stolow(b, c, d),Michael S. Schuurman(b, d),

a A. A. Noyes Laboratory of Chemical Physics, California Institute of Technology, Pasadena, California 91125, USA

b National Research Council Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6, Canada

c Department of Physics, University of Ottawa, ON K1N 6N5 Canada

d Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, ON, K1N 6N5, Canada

Highlights

• Time-resolved photoelectron angular distributions around conical intersections are studied.
• Ab initio multiple spawning method is applied to obtain wavepacket densities.
• Geometry and energy dependent photoelectron matrix elements are employed.
• Molecular and laboratory photoelectron angular distributions are used to illustrate the non-adiabatic dynamics.
• Photoelectron spectra are compared with measured values.

Abstract

We report results from a novel fully ab initio method for simulating the time-resolved photoelectron angular distributions around conical intersections in CS2. The technique employs wavepacket densities obtained with the multiple spawning method in conjunction with geometry- and energy-dependent photoionization matrix elements. The robust agreement of the calculated molecular-frame photoelectron angular distributions with measured values for CS2 demonstrates that this approach can successfully illuminate, and disentangle, the underlying coupled nuclear and electronic dynamics around conical intersections in polyatomic molecules.

DOI: 10.1016/j.cplett.2017.02.014

Time-resolved multi-mass ion imaging: femtosecond UV-VUV pump-probe spectroscopy with the PImMS camera

Time-resolved multi-mass ion imaging: femtosecond UV-VUV pump-probe spectroscopy with the PImMS camera

UPDATE: 4th April 2017

The article is now published in the Journal of Chemical Physics, with an accompanying press release, The Inner Lives of Molecules, from AIP.

The full dataset and analysis scripts are now also available via OSF, DOI: 10.17605/OSF.IO/RRFK3.

Feb. 2017 – new article on the arXiv:

Time-resolved multi-mass ion imaging: femtosecond UV-VUV pump-probe spectroscopy with the PImMS camera

The Pixel-Imaging Mass Spectrometry (PImMS) camera allows for 3D charged particle imaging measurements, in which the particle time-of-flight is recorded along with (x,y) position. Coupling the PImMS camera to an ultrafast pump-probe velocity-map imaging spectroscopy apparatus therefore provides a route to time-resolved multi-mass ion imaging, with both high count rates and large dynamic range, thus allowing for rapid measurements of complex photofragmentation dynamics. Furthermore, the use of vacuum ultraviolet wavelengths for the probe pulse allows for an enhanced observation window for the study of excited state molecular dynamics in small polyatomic molecules having relatively high ionization potentials. Herein, preliminary time-resolved multi-mass imaging results from C2F3I photolysis are presented. The experiments utilized femtosecond UV and VUV (160.8~nm and 267~nm) pump and probe laser pulses in order to demonstrate and explore this new time-resolved experimental ion imaging configuration. The data indicates the depth and power of this measurement modality, with a range of photofragments readily observed, and many indications of complex underlying wavepacket dynamics on the excited state(s) prepared.

arXiv 1702.00744 (2017)

Now published in JCP:
The Journal of Chemical Physics 147, 013911 (2017);
DOI: http://dx.doi.org/10.1063/1.4978923

Also on Authorea, DOI: 10.22541/au.149030711.19068540

 

 

Ultrafast atomic and molecular physics with cutting-edge light sources: New opportunities and challenges

Ultrafast atomic and molecular physics with cutting-edge light sources: New opportunities and challenges

Originally presented at ITAMP’s (Institute for Theoretical, Atomic and Molecular and Optical Physics, part of the Harvard-Smithsonian Center for Astrophysics) workshop on Ultrafast atomic and molecular physics with cutting-edge light sources: New opportunities and challenges, back in Nov. 2013.

Thanks to ITAMP for the video!

 

General phenomenology of ionization from aligned molecular ensembles (with video)

General phenomenology of ionization from aligned molecular ensembles (with video)

Paul Hockett
New J. Phys. 17 023069 2015

Single and multi-photon ionization of aligned molecular ensembles is examined, with a particular focus on the link between the molecular axis distribution and observable in various angle-integrated and angle-resolved measurements. To maintain generality the problem is treated geometrically, with the aligned ensemble cast in terms of axis distribution moments, and the response of observables in terms of couplings to these moments. Within this formalism the angular momentum coupling is treated analytically, allowing for general characteristics—independent of the details of the ionization dynamics of a specific molecule—to be determined. Limiting cases are explored in order to provide a phenomenology which should be readily applicable to a range of experimental measurements, and illustrate how observables can be sensitive to fine details of the alignment, i.e. higher-order moments of the axis distribution, which are often neglected in experimental studies. We hope that this detailed and comprehensive treatment will bridge the gap between existing theoretical and experimental works, and provide both quantitative physical insights and a useful general phenomenology for researchers working with aligned molecular ensembles.

Full article PDF

DOI: 10.1088/1367-2630/17/2/023069