Molecular Frame Photoelectron Angular Distributions in Polyatomic Molecules from Lab Frame Coherent Rotational Wavepacket Evolution

Molecular Frame Photoelectron Angular Distributions in Polyatomic Molecules from Lab Frame Coherent Rotational Wavepacket Evolution

Margaret Gregory, Paul Hockett, Albert Stolow, Varun Makhija

arXiv:2012.04561, Dec. 2020

The application of a matrix-based reconstruction protocol for obtaining Molecular Frame (MF) photoelectron angular distributions (MFPADs) from laboratory frame (LF) measurements (LFPADs) is explored. Similarly to other recent works on the topic of MF reconstruction, this protocol makes use of time-resolved LF measurements, in which a rotational wavepacket is prepared and probed via photoionization, followed by a numerical reconstruction routine; however, in contrast to other methodologies, the protocol developed herein does not require determination of photoionization matrix elements, and consequently takes a relatively simple numerical form (matrix transform making use of the Moore-Penrose inverse). Significantly, the simplicity allows application of the method to the successful reconstruction of MFPADs for polyatomic molecules. The scheme is demonstrated numerically for two realistic cases, N2 and C2H4. The new technique is expected to be generally applicable for a range of MF reconstruction problems involving photoionization of polyatomic molecules.


 

Photoelectron angular distributions from resonant two-photon ionisation of adiabatically aligned naphthalene and aniline molecules

Photoelectron angular distributions from resonant two-photon ionisation of adiabatically aligned naphthalene and aniline molecules

Molecular Physics, Article: e1836411 | Received 03 Aug 2020, Accepted 06 Oct 2020, Published online: 22 Oct 2020,
https://doi.org/10.1080/00268976.2020.1836411

Photoelectron images have been measured following the ionisation of aligned distributions of gas phase naphthalene and aniline molecules. Alignment in the adiabatic regime was achieved by interaction with a 100 ps infrared laser pulse, with ionisation achieved in a two-photon resonant scheme using a low intensity UV pulse of ∼6 ps duration. The resulting images are found to exhibit anisotropy that increases when the alignment pulse is present, with the aniline PADs peaking along the polarisation vector of the ionising light and the naphthalene PADs developing a characteristic four-lobed structure. Photoelectron angular distributions (PADs) that result from the ionisation of unaligned and fully aligned distributions of molecules are calculated using the ePolyScat ab initio suite and converted into two-dimensional photoelectron images. In the case of naphthalene excellent agreement is observed between experiment and the simulation for the fully aligned distribution, showing that the alignment step allows us to probe the molecular frame, but in the case of aniline it is clear that additional processes occur following the one-photon resonant step.

Spectroscopic and Structural Probing of Excited-State Molecular Dynamics with Time-Resolved Photoelectron Spectroscopy and Ultrafast Electron Diffraction

Spectroscopic and Structural Probing of Excited-State Molecular Dynamics with Time-Resolved Photoelectron Spectroscopy and Ultrafast Electron Diffraction

Yusong Liu, Spencer L. Horton, Jie Yang, J. Pedro F. Nunes, Xiaozhe Shen, Thomas J. A. Wolf, Ruaridh Forbes, Chuan Cheng, Bryan Moore, Martin Centurion, Kareem Hegazy, Renkai Li, Ming-Fu Lin, Albert Stolow, Paul Hockett, Tamás Rozgonyi, Philipp Marquetand, Xijie Wang, and Thomas Weinacht
Phys. Rev. X 10, 021016 – Published 22 April 2020

DOI: 10.1103/PhysRevX.10.021016

Pump-probe measurements aim to capture the motion of electrons and nuclei on their natural timescales (femtoseconds to attoseconds) as chemical and physical transformations take place, effectively making “molecular movies” with short light pulses. However, the quantum dynamics of interest are filtered by the coordinate-dependent matrix elements of the chosen experimental observable. Thus, it is only through a combination of experimental measurements and theoretical calculations that one can gain insight into the internal dynamics. Here, we report on a combination of structural (relativistic ultrafast electron diffraction, or UED) and spectroscopic (time-resolved photoelectron spectroscopy, or TRPES) measurements to follow the coupled electronic and nuclear dynamics involved in the internal conversion and photodissociation of the polyatomic molecule, diiodomethane (CH2I2). While UED directly probes the 3D nuclear dynamics, TRPES only serves as an indirect probe of nuclear dynamics via Franck-Condon factors, but it is sensitive to electronic energies and configurations, via Koopmans’ correlations and photoelectron angular distributions. These two measurements are interpreted with trajectory surface hopping calculations, which are capable of simulating the observables for both measurements from the same dynamics calculations. The measurements highlight the nonlocal dynamics captured by different groups of trajectories in the calculations. For the first time, both UED and TRPES are combined with theory capable of calculating the observables in both cases, yielding a direct view of the structural and nonadiabatic dynamics involved.

Fibre VUV generation & applications

Fibre VUV generation & applications

Over the last few months (summer 2018) a new project has been shaping up, in collaboration with colleagues from the PCF division (Russell research group) at MPL.  The aim is to develop new ultrafast experiments based on their hollow-core PCFs, which can be used to provide tuneable UV and VUV. This work is part of our larger source development project, and will develop towards applications in photoelectron metrology and quantum optics (amongst others!).

More details to follow, but for now here are a few images of the work in progress…

Quantum Metrology with Photoelectrons (book)

Quantum Metrology with Photoelectrons (book)

Update April 2018 – the books are now available via IOP, see details at end of post.

Book for IOP Concise Physics series, due early 2018

Dr. Paul Hockett

National Research Council of Canada

Online resources

OSF project (ID: q2v3g) with interactive content and additional resources, DOI: 10.17605/OSF.IO/Q2V3G

femtolab.ca website, posts tagged “metrology-book”

femtolab.ca website, posts tagged “video”

Abstract

Photoionization is an interferometric process, in which multiple paths can contribute to the final continuum photoelectron wavefunction. At the simplest level, interferences between different final angular momentum states are manifest in the energy and angle resolved photoelectron spectra: metrology schemes making use of these interferograms are thus phase-sensitive, and provide a powerful route to detailed understanding of photoionization. In these cases, the continuum wavefunction (and underlying scattering dynamics) can be characterised. At a more complex level, such measurements can also provide a powerful probe for other processes of interest, leading to a more general class of quantum metrology built on phase-sensitive photoelectron imaging.  Since the turn of the century, the increasing availability of photoelectron imaging experiments, along with the increasing sophistication of experimental techniques, and the availability of computational resources for analysis and numerics, has allowed for significant developments in such photoelectron metrology.

Volume I covers the core physics of photoionization, including a range of computational examples. The material is presented as both reference and tutorial, and should appeal to readers of all levels.  Volume II explores applications, and the development of quantum metrology schemes based on photoelectron measurements. The material is more technical, and will appeal more to the specialist reader.

Full text

Quantum Metrology with Photoelectrons

Volume 1
ISBN 978-1-6817-4684-5
http://iopscience.iop.org/book/978-1-6817-4684-5
Volume 2
ISBN 978-1-6817-4688-3
http://iopscience.iop.org/book/978-1-6817-4688-3

 

Bootstrapping (Ultrafast) Photoionization Dynamics – PQE 2018 (extended) video

Bootstrapping (Ultrafast) Photoionization Dynamics – PQE 2018 (extended) video

Bootstrapping (Ultrafast) Photoionization Dynamics – PQE 2018 (extended) from femtolab.ca on Vimeo.

Talk originally given as a 20min presentation at PQE 2018 (Snowbird, Utah, http://pqeconference.com/pqe2018/program). The original talk was not recorded; this is an extended version using the same slides, but with rather more introductory discussion. The abstract is given below, along with links to additional material.

More details of the work discussed in the main part of the talk can be found in:
Molecular Frame Reconstruction Using Time-Domain Photoionization Interferometry.
Marceau et. al., Physical Review Letters, 119(8), 83401 (2017).
http://doi.org/10.1103/PhysRevLett.119.083401

PQE 2018 Abstract

Bootstrapping (Ultrafast) Photoionization Dynamics
Slot: Tuesday Morning Invited Session 1
Session: Ultrafast photoionization dynamics

Photoionization is an interferometric process, in which multiple paths can contribute to the final continuum photoelectron state. At the simplest level, interferences between different final angular momentum states are clearly manifest in the energy and angle resolved photoelectron spectra; metrology schemes making use of these interferograms are thus phase-sensitive, and provide a powerful route to detailed understanding of photoionization.

The high information content of angle-resolved interferograms, combined with geometric control over the photoionization dynamics, can provide sufficient data for reconstruction of the continuum state, in terms of the constituent partial waves and phases. This has recently been explored for a range of cases, including the use of ultrafast pump-probe schemes with a bootstrapping analysis methodology: aspects of this work will be presented.

DOI: 10.6084/m9.figshare.5645509

Refs
Molecular Frame Reconstruction Using Time-Domain Photoionization Interferometry
Marceau, C., Makhija, V., Platzer, D., Naumov, A. Y., Corkum, P. B., Stolow, A., Villeneuve, D. M., Hockett, P. (2017). Physical Review Letters, 119(8), 83401. http://doi.org/10.1103/PhysRevLett.119.083401

Coherent control of photoelectron wavepacket angular interferograms.
Hockett, P., Wollenhaupt, M., & Baumert, T. (2015). Journal of Physics B: Atomic, Molecular and Optical Physics, 48(21), 214004. http://doi.org/10.1088/0953-4075/48/21/214004

Complete Photoionization Experiments via Ultrafast Coherent Control with Polarization Multiplexing.
Hockett, P., Wollenhaupt, M., Lux, C., & Baumert, T. (2014). Physical Review Letters, 112(22), 223001. http://doi.org/10.1103/PhysRevLett.112.223001

Coherent imaging of an attosecond electron wave packet.
Villeneuve, D. M., Hockett, P., Vrakking, M. J. J., & Niikura, H. (2017). Science, 356(6343), 1150–1153. http://doi.org/10.1126/science.aam8393

Bootstrapping to the Molecular Frame with Time-domain Photoionization Interferometry

Bootstrapping to the Molecular Frame with Time-domain Photoionization Interferometry

Update Jan 2018 – a presentation covering this work was given at the PQE conference, video and slides are available online.

Update August 2017 – this article is now published in PRL, under the alternative title Molecular Frame Reconstruction Using Time-Domain Photoionization Interferometry.
Phys. Rev. Lett. 119, 083401 (2017), DOI: 10.1103/PhysRevLett.119.083401

(Feb 2017) New manuscript on the arxiv:

Bootstrapping to the Molecular Frame with Time-domain Photoionization Interferometry

 

Photoionization of molecular species is, essentially, a multi-path interferometer with both experimentally controllable and intrinsic molecular characteristics. In this work, XUV photoionization of impulsively aligned molecular targets (N2) is used to provide a time-domain route to “complete” photoionization experiments, in which the rotational wavepacket controls the geometric part of the photoionization interferometer. The data obtained is sufficient to determine the magnitudes and phases of the ionization matrix elements for all observed channels, and to reconstruct molecular frame interferograms from lab frame measurements. In principle this methodology provides a time-domain route to complete photoionization experiments, and the molecular frame, which is generally applicable to any molecule (no prerequisites), for all energies and ionization channels.

arxiv 1701.08432 (2017)

Supplementary material (theory, data and code) available at DOI: 10.6084/m9.figshare.4480349.

Photoionization Interferometry & Metrology

Photoionization Interferometry & Metrology

Photoionization is a complex quantum mechanical process, with a range of interfering channels playing a role in even the simplest case. For problems in quantum metrology and sensing, a detailed understanding of the process is desirable for accurate measurements; quantum control is also a possible outcome of such understanding. New research in this area will build on recent cutting-edge work at NRC (see below), which probed the fundamental quantum physics of photoionization in atoms and molecules, and metrology work which demonstrated the retrieval of electron wavefunctions via interferometric time-domain measurements.

Four areas of photoionization interferometry are the target of current research:

  1. Metrology and control with rotational wavepackets.
  2. Metrology and control with shaped laser pulses.
  3. Quantum dynamics probed via photoionization interferometry.
  4. Fundamental properties of photoion and photoelectron coherence.

Depending on interests and experience, project work will be in one (or more) of these areas.

An introduction to this topic, and recent work, can be found in Paul’s DAMOP 2017 talk Phase-sensitive Photoelectron Metrology (below), and via our blog.

Phase-sensitive Photoelectron Metrology – Dr. P. Hockett, presentation at DAMOP 2017 from femtolab.ca on Vimeo.