Report/Journal Article

PUBDB-2018-01916

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Mapping the Complete Reaction Path of a Complex Photochemical Reaction

Smith, A. D. ; Warne, E. M. ; Bellshaw, D. ; Horke, D.CFEL*DESY* ; Tudorovskya, M. ; Springate, E. ; Jones, A. J. H. ; Cacho, C. ; Chapman, R. T. ; Kirrander, A. (Corresponding author) ; Minns, R. S. (Corresponding author)

2018
APS College Park, Md.

This record in other databases:        

Please use a persistent id in citations: doi:10.1103/PhysRevLett.120.183003  doi:10.3204/PUBDB-2018-01916

Report No.: arXiv:1805.02170

Abstract: We probe the dynamics of dissociating $CS^2$ molecules across the entire reaction pathway upon excitation. Photoelectron spectroscopy measurements using laboratory-generated femtosecond extreme ultraviolet pulses monitor the competing dissociation, internal conversion, and intersystem crossing dynamics. Dissociation occurs either in the initially excited singlet manifold or, via intersystem crossing, in the triplet manifold. Both product channels are monitored and show that, despite being more rapid, the singlet dissociation is the minor product and that triplet state products dominate the final yield. We explain this by a consideration of accurate potential energy curves for both the singlet and triplet states. We propose that rapid internal conversion stabilizes the singlet population dynamically, allowing for singlet-triplet relaxation via intersystem crossing and the efficient formation of spin-forbidden dissociation products on longer timescales. The study demonstrates the importance of measuring the full reaction pathway for defining accurate reaction mechanisms.

Note: © American Physical Society

---

Contributing Institute(s):

1. CFEL-Coherent X-Ray Imaging (FS-CFEL-1)
2. Controlled Molecule Imaging (FS-CFEL-CMI)

Research Program(s):

1. 6211 - Extreme States of Matter: From Cold Ions to Hot Plasmas (POF3-621) (POF3-621)
2. CUI - Hamburger Zentrum für ultraschnelle Beobachtung (194651731) (194651731)
3. COMOTION - Controlling the Motion of Complex Molecules and Particles (614507) (614507)
4. LASERLAB-EUROPE - The Integrated Initiative of European Laser Research Infrastructures II (228334) (228334)
5. NEWLIGHT - New Light on Chemical Dynamics (618902) (618902)

Experiment(s):

1. Measurement at external facility

Appears in the scientific report 2018

---

Database coverage:
; ; ; Current Contents - Physical, Chemical and Earth Sciences ; Ebsco Academic Search ; IF >= 5 ; JCR ; NCBI Molecular Biology Database ; Nationallizenz ; SCOPUS ; Science Citation Index ; Science Citation Index Expanded ; Thomson Reuters Master Journal List ; Web of Science Core Collection

---