Time-resolved ab initio chemistry: wavepackets and observables for Carbon Disulphide (CS2) --------------------------------------------------- Overview -------- The computations described herein model time-resolved pump-probe experiments at 200 nm, which prepared a vibronic wavepacket on the C state of CS2, and measured time, energy and angle-resolved photoelectron data. See publications below for further details. The calculations combine excited state wavepackets calculated using the ab initio multiple spawning (AIMS) technique ([M. Schuurman][1], NRC) with full (energy and geometry dependent) photoionization calculations ([K. Wang][2] & [V. McKoy][3], CALTECH). The documents herein provide details of the methodology used to obtain TRPES and TRPADs from the computational data, results and visualisations ([P. Hockett][4], NRC). ---------- **TRPES results** (a) Expt (top) & calculated (bottom) TRPES; (b) slices through the TRPES. ![(a) Expt (top) & calculated (bottom) TRPES; (b) slices through the TRPES][5] ---------- **TRPADs results** (a) Calculated TRPADs (0.7eV) (b), (c) Comparison with expt. TRPADs (discrete times). ![(a) Calculated TRPADs (0.7eV) (b), (c) Comparison with expt. TRPADs ][6] Details ------- This OSF project collects results and notes from calculations & analysis (NRC and Caltech), 2013-2017. Some aspects of these results are now published (see below), but a significant portion of this work remains unpublished for various reasons. This project collects a range of the results & working documents in order to make the ongoing/unpublished parts of the work open and accessible. Introductory docs (start here): - [CS2 calculations summary (12th Feb 2014)][7]: computational results and comparison with experiment (time-resolved photoelectron spectra, time-resolved photoelectron angular distributions and beta parameters. - [CS2 calculations summary (23rd April 2014)][8]: full detail of the computational results, including visualisation of both wavepackets and observables. - [CS2 wavepackets & TRPADs][9]: Details of the formalism applied for couping the ionization matrix element calculations (Wang & McKoy) to the AIMS wavepackets (Schuurman). - [CS2 wavepacket calculations - overview][10]: Overview of the AIMS wavepackets. For further details [see the full docs. list.][11] Publications ------------ Publications from this work, see these for a more formal introduction, and detailed presentation of some aspects of this work. ---------- **[Monitoring Non-adiabatic Dynamics in CS2 with Time- and Energy-Resolved Photoelectron Spectra of Wavepackets][12]** Kwanghsi Wang, Vincent McKoy, Paul Hockett, Albert Stolow, Michael S. Schuurman Chem. Phys. Lett. (in press, 2017), [DOI: 10.1016/j.cplett.2017.02.014][13] **[Time-Resolved Photoelectron Spectra of CS2: Dynamics at Conical Intersections][14]** Kwanghsi Wang, Vincent McKoy, Paul Hockett, and Michael S. Schuurman Phys. Rev. Lett. 112, 113007 (2014), [DOI: 10.1103/PhysRevLett.112.113007][15] ---------- Original experimental work, which inspired this study: **[Time-resolved imaging of purely valence-electron dynamics during a chemical reaction][16]** Paul Hockett, Christer Z. Bisgaard, Owen J. Clarkin & Albert Stolow Nature Physics 7, 612–615 (2011), [DOI: 10.1038/nphys1980][17] **[Time-Resolved Molecular Frame Dynamics of Fixed-in-Space CS2 Molecules][18]** Christer Z. Bisgaard, Owen J. Clarkin, Guorong Wu, Anthony M. D. Lee, Oliver Geßner, Carl C. Hayden, Albert Stolow Science 323, 1464-1468 (2009) [DOI: 10.1126/science.1169183][19] [1]: https://science.uottawa.ca/chemistry/people/schuurman-michael [2]: https://scholar.google.ca/scholar?hl=en&q=Kwanghsi+wang+caltech&btnG=&as_sdt=1%2C5&as_sdtp= [3]: http://cce.caltech.edu/content/vincent-b-mckoy [4]: http://orcid.org/0000-0001-9561-8433 [5]: https://mfr.osf.io/export?url=https://osf.io/v5kmn/?action=download&direct&mode=render&initialWidth=848&childId=mfrIframe&format=1200x1200.jpeg [6]: https://mfr.osf.io/export?url=https://osf.io/sqfjm/?action=download&direct&mode=render&initialWidth=848&childId=mfrIframe&format=1200x1200.jpeg [7]: https://osf.io/ug2dm/ [8]: https://osf.io/pyudq/ [9]: https://osf.io/9jzm2/ [10]: https://osf.io/uknd3/ [11]: https://osf.io/rjmpd/wiki/Document%20details/ [12]: http://doi.org/10.1016/j.cplett.2017.02.014 [13]: http://doi.org/10.1016/j.cplett.2017.02.014 [14]: https://doi.org/10.1103/PhysRevLett.112.113007 [15]: https://doi.org/10.1103/PhysRevLett.112.113007 [16]: http://dx.doi.org/10.1038/nphys1980 [17]: http://dx.doi.org/10.1038/nphys1980 [18]: http://dx.doi.org/10.1126/science.1169183 [19]: http://dx.doi.org/10.1126/science.1169183