Ultrafast relaxation of photoexcited superfluid He nanodroplets
Abstract
The relaxation of photoexcited nanosystems is a fundamental process of light-matter interaction. Depending on the couplings of the internal degrees of freedom, relaxation can be ultrafast, converting electronic energy in a few fs, or slow, if the energy is trapped in a metastable state that decouples from its environment. Here, we study helium nanodroplets excited resonantly by femtosecond extreme-ultraviolet (XUV) pulses from a seeded free-electron laser. Despite their superfluid nature, we find that helium nanodroplets in the lowest electronically excited states undergo ultrafast relaxation. By comparing experimental photoelectron spectra with time-dependent density functional theory simulations, we unravel the full relaxation pathway: Following an ultrafast interband transition, a void nanometer-sized bubble forms around the localized excitation (He*) within 1 ps. Subsequently, the bubble collapses and releases metastable He* at the droplet surface. This study highlights the high level of detail achievable in probing the photodynamics of nanosystems using tunable XUV pulses.
- Authors:
-
more »
- Aarhus Univ. (Denmark)
- Univ. of Freiburg, Freiburg im Breisgau (Germany); Univ. of Connecticut, Storrs, CT (United States)
- Central European Research Infrastructure Consortium (CERIC–ERIC), Trieste (Italy); Italian National Research Council (CNR), Monterotondo Scalo (Italy)
- Italian National Research Council (CNR), Monterotondo Scalo (Italy)
- Elettra Sincrotrone Trieste (Italy)
- Italian National Research Council (CNR), Trieste (Italy); Univ. degli Studi, Milan (Italy)
- Ecole Polytechnique Fédérale de Lausanne (EPFL), Lausanne (Switzerland)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Italian National Research Council (CNR), Trieste (Italy)
- Kido Dynamics, Lausanne (Switzerland); Inst. de Fisica Interdisciplinar y Sistemas Complejos, Palma de Mallorca (Spain)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
- European X-Ray Free-Electron Laser Facility (XFEL), Schenefeld (Germany); Inst. für Optik und Atomare Physik, Berlin (Germany)
- Univ. degli Studi, Milan (Italy)
- Inst. für Optik und Atomare Physik, Berlin (Germany)
- California State Univ., Northridge, CA (United States)
- Univ. de Barcelona (Spain)
- Univ. de Barcelona (Spain); Univ. Paul Sabatier-Toulouse (France)
- Univ. of Freiburg, Freiburg im Breisgau (Germany)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; German Research Foundation (DFG); National Science Foundation (NSF); Carl-Zeiss-Stiftung; Swiss National Science Foundation (SNSF)
- OSTI Identifier:
- 1599845
- Grant/Contract Number:
- AC02-05CH11231; DMR-1828019; FIS2017-87801-P
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Communications
- Additional Journal Information:
- Journal Volume: 11; Journal Issue: 1; Journal ID: ISSN 2041-1723
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 74 ATOMIC AND MOLECULAR PHYSICS; atomic and molecular interactions with photons; macromolecules and clusters
Citation Formats
Mudrich, M., LaForge, A. C., Ciavardini, A., O’Keeffe, P., Callegari, C., Coreno, M., Demidovich, A., Devetta, M., Fraia, M. Di, Drabbels, M., Finetti, P., Gessner, O., Grazioli, C., Hernando, A., Neumark, D. M., Ovcharenko, Y., Piseri, P., Plekan, O., Prince, K. C., Richter, R., Ziemkiewicz, M. P., Möller, T., Eloranta, J., Pi, M., Barranco, M., and Stienkemeier, F. Ultrafast relaxation of photoexcited superfluid He nanodroplets. United States: N. p., 2020.
Web. doi:10.1038/s41467-019-13681-6.
Mudrich, M., LaForge, A. C., Ciavardini, A., O’Keeffe, P., Callegari, C., Coreno, M., Demidovich, A., Devetta, M., Fraia, M. Di, Drabbels, M., Finetti, P., Gessner, O., Grazioli, C., Hernando, A., Neumark, D. M., Ovcharenko, Y., Piseri, P., Plekan, O., Prince, K. C., Richter, R., Ziemkiewicz, M. P., Möller, T., Eloranta, J., Pi, M., Barranco, M., & Stienkemeier, F. Ultrafast relaxation of photoexcited superfluid He nanodroplets. United States. doi:https://doi.org/10.1038/s41467-019-13681-6
Mudrich, M., LaForge, A. C., Ciavardini, A., O’Keeffe, P., Callegari, C., Coreno, M., Demidovich, A., Devetta, M., Fraia, M. Di, Drabbels, M., Finetti, P., Gessner, O., Grazioli, C., Hernando, A., Neumark, D. M., Ovcharenko, Y., Piseri, P., Plekan, O., Prince, K. C., Richter, R., Ziemkiewicz, M. P., Möller, T., Eloranta, J., Pi, M., Barranco, M., and Stienkemeier, F. Wed .
"Ultrafast relaxation of photoexcited superfluid He nanodroplets". United States. doi:https://doi.org/10.1038/s41467-019-13681-6. https://www.osti.gov/servlets/purl/1599845.
@article{osti_1599845,
title = {Ultrafast relaxation of photoexcited superfluid He nanodroplets},
author = {Mudrich, M. and LaForge, A. C. and Ciavardini, A. and O’Keeffe, P. and Callegari, C. and Coreno, M. and Demidovich, A. and Devetta, M. and Fraia, M. Di and Drabbels, M. and Finetti, P. and Gessner, O. and Grazioli, C. and Hernando, A. and Neumark, D. M. and Ovcharenko, Y. and Piseri, P. and Plekan, O. and Prince, K. C. and Richter, R. and Ziemkiewicz, M. P. and Möller, T. and Eloranta, J. and Pi, M. and Barranco, M. and Stienkemeier, F.},
abstractNote = {The relaxation of photoexcited nanosystems is a fundamental process of light-matter interaction. Depending on the couplings of the internal degrees of freedom, relaxation can be ultrafast, converting electronic energy in a few fs, or slow, if the energy is trapped in a metastable state that decouples from its environment. Here, we study helium nanodroplets excited resonantly by femtosecond extreme-ultraviolet (XUV) pulses from a seeded free-electron laser. Despite their superfluid nature, we find that helium nanodroplets in the lowest electronically excited states undergo ultrafast relaxation. By comparing experimental photoelectron spectra with time-dependent density functional theory simulations, we unravel the full relaxation pathway: Following an ultrafast interband transition, a void nanometer-sized bubble forms around the localized excitation (He*) within 1 ps. Subsequently, the bubble collapses and releases metastable He* at the droplet surface. This study highlights the high level of detail achievable in probing the photodynamics of nanosystems using tunable XUV pulses.},
doi = {10.1038/s41467-019-13681-6},
journal = {Nature Communications},
number = 1,
volume = 11,
place = {United States},
year = {2020},
month = {1}
}
Works referenced in this record:
Electronic excitations in liquid helium: The evolution from small clusters to large droplets
journal, October 1993
- Joppien, M.; Karnbach, R.; Möller, T.
- Physical Review Letters, Vol. 71, Issue 16
Imaging Excited-State Dynamics of Doped He Nanodroplets in Real-Time
journal, December 2016
- von Vangerow, Johannes; Coppens, François; Leal, Antonio
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 1
Coherently wired light-harvesting in photosynthetic marine algae at ambient temperature
journal, February 2010
- Collini, Elisabetta; Wong, Cathy Y.; Wilk, Krystyna E.
- Nature, Vol. 463, Issue 7281
Interaction of Helium Rydberg State Atoms with Superfluid Helium
journal, December 2013
- Fiedler, Steven L.; Eloranta, Jussi
- Journal of Low Temperature Physics, Vol. 174, Issue 5-6
Three-Dimensional Shapes of Spinning Helium Nanodroplets
journal, December 2018
- Langbehn, Bruno; Sander, Katharina; Ovcharenko, Yevheniy
- Physical Review Letters, Vol. 121, Issue 25
Laser-Induced Rotation of Iodine Molecules in Helium Nanodroplets: Revivals and Breaking Free
journal, May 2017
- Shepperson, Benjamin; Søndergaard, Anders A.; Christiansen, Lars
- Physical Review Letters, Vol. 118, Issue 20
Coupled cluster methods including triple excitations for excited states of radicals
journal, February 2005
- Smith, Christopher E.; King, Rollin A.; Crawford, T. Daniel
- The Journal of Chemical Physics, Vol. 122, Issue 5
Nature of the excited states of
journal, October 1975
- Guberman, Steven L.; Goddard, William A.
- Physical Review A, Vol. 12, Issue 4
Molpro: a general-purpose quantum chemistry program package: Molpro
journal, July 2011
- Werner, Hans-Joachim; Knowles, Peter J.; Knizia, Gerald
- Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 2
Spectroscopy and dynamics in helium nanodroplets
journal, April 2006
- Stienkemeier, Frank; Lehmann, Kevin K.
- Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 39, Issue 8
Translational dynamics of photoexcited atoms in 4He nanodroplets: the case of silver
journal, January 2013
- Mateo, David; Hernando, Alberto; Barranco, Manuel
- Physical Chemistry Chemical Physics, Vol. 15, Issue 42
Ultrafast probing of ejection dynamics of Rydberg atoms and molecular fragments from electronically excited helium nanodroplets
journal, December 2012
- Bünermann, Oliver; Kornilov, Oleg; Haxton, Daniel J.
- The Journal of Chemical Physics, Vol. 137, Issue 21
Desorption of alkali atoms from 4He nanodroplets
journal, January 2012
- Hernando, Alberto; Barranco, Manuel; Pi, Martí
- Physical Chemistry Chemical Physics, Vol. 14, Issue 11
Internally contracted multiconfiguration-reference configuration interaction calculations for excited states
journal, October 1992
- Knowles, Peter J.; Werner, Hans-Joachim
- Theoretica Chimica Acta, Vol. 84, Issue 1-2
Femtosecond photoexcitation dynamics inside a quantum solvent
journal, October 2018
- Thaler, Bernhard; Ranftl, Sascha; Heim, Pascal
- Nature Communications, Vol. 9, Issue 1
Rapidly pulsed helium droplet source
journal, April 2009
- Pentlehner, Dominik; Riechers, Ricarda; Dick, Bernhard
- Review of Scientific Instruments, Vol. 80, Issue 4
Coupled Electronic and Structural Relaxation Pathways in the Postexcitation Dynamics of Rydberg States of Clusters
journal, September 2014
- Masson, A.; Heitz, M. -C.; Mestdagh, J. -M.
- Physical Review Letters, Vol. 113, Issue 12
Direct observation of ring-opening dynamics in strong-field ionized selenophene using femtosecond inner-shell absorption spectroscopy
journal, December 2016
- Lackner, Florian; Chatterley, Adam S.; Pemmaraju, C. D.
- The Journal of Chemical Physics, Vol. 145, Issue 23
Theoretical study of the radiative lifetime for the spin‐forbidden transition a 3 Σ + u → X 1 Σ + g in He 2
journal, February 1989
- Chabalowski, Cary F.; Jensen, James O.; Yarkony, David R.
- The Journal of Chemical Physics, Vol. 90, Issue 4
Two-dimensional charged particle image inversion using a polar basis function expansion
journal, November 2004
- Garcia, Gustavo A.; Nahon, Laurent; Powis, Ivan
- Review of Scientific Instruments, Vol. 75, Issue 11
Femtosecond time-resolved XUV + UV photoelectron imaging of pure helium nanodroplets
journal, November 2014
- Ziemkiewicz, Michael P.; Bacellar, Camila; Siefermann, Katrin R.
- The Journal of Chemical Physics, Vol. 141, Issue 17
Electronic excitation, decay and photochemical processes in rare gas clusters
journal, January 1995
- Karnbach, R.; Joppien, M.; Möllef, T.
- Journal de Chimie Physique, Vol. 92
A modular end-station for atomic, molecular, and cluster science at the low density matter beamline of FERMI@Elettra
journal, August 2013
- Lyamayev, Viktor; Ovcharenko, Yevheniy; Katzy, Raphael
- Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 46, Issue 16
Theoretical investigation of the a 3 Σ + u , A 1 Σ + u , c 3 Σ + g , and C 1 Σ + g potential energy curves of He 2 and of He*(2 1 S , 2 3 S )+He scattering
journal, May 1983
- Sunil, K. K.; Lin, J.; Siddiqui, H.
- The Journal of Chemical Physics, Vol. 78, Issue 10
Femtosecond Photoelectron Imaging of Transient Electronic States and Rydberg Atom Emission from Electronically Excited He Droplets
journal, July 2011
- Kornilov, Oleg; Bünermann, Oliver; Haxton, Daniel J.
- The Journal of Physical Chemistry A, Vol. 115, Issue 27
The CC3 model: An iterative coupled cluster approach including connected triples
journal, February 1997
- Koch, Henrik; Christiansen, Ove; Jo/rgensen, Poul
- The Journal of Chemical Physics, Vol. 106, Issue 5
Vibrational relaxation and dephasing of Rb2 attached to helium nanodroplets
journal, January 2011
- Grüner, B.; Schlesinger, M.; Heister, Ph.
- Physical Chemistry Chemical Physics, Vol. 13, Issue 15
Site- and energy-selective slow-electron production through intermolecular Coulombic decay
journal, December 2013
- Gokhberg, Kirill; Kolorenč, Přemysl; Kuleff, Alexander I.
- Nature, Vol. 505, Issue 7485
Relaxation mechanisms of UV-photoexcited DNA and RNA nucleobases
journal, November 2010
- Barbatti, M.; Aquino, A. J. A.; Szymczak, J. J.
- Proceedings of the National Academy of Sciences, Vol. 107, Issue 50
Photoelectron Imaging of Helium Droplets
journal, July 2003
- Peterka, Darcy S.; Lindinger, Albrecht; Poisson, Lionel
- Physical Review Letters, Vol. 91, Issue 4
Simulations of the dissociation of small helium clusters with ab initio molecular dynamics in electronically excited states
journal, April 2014
- Closser, Kristina D.; Gessner, Oliver; Head-Gordon, Martin
- The Journal of Chemical Physics, Vol. 140, Issue 13
Coherent diffractive imaging of single helium nanodroplets with a high harmonic generation source
journal, September 2017
- Rupp, Daniela; Monserud, Nils; Langbehn, Bruno
- Nature Communications, Vol. 8, Issue 1
Heterogeneous Photochemistry in the Atmosphere
journal, February 2015
- George, Christian; Ammann, Markus; D’Anna, Barbara
- Chemical Reviews, Vol. 115, Issue 10
Light-Harvesting and Ultrafast Energy Migration in Porphyrin-Based Metal–Organic Frameworks
journal, December 2012
- Son, Ho-Jin; Jin, Shengye; Patwardhan, Sameer
- Journal of the American Chemical Society, Vol. 135, Issue 2
Dynamics of the Formation of an Electron Bubble in Liquid Helium
journal, November 1995
- Rosenblit, Michael; Jortner, Joshua
- Physical Review Letters, Vol. 75, Issue 22
Helium Nanodroplets: An Overview
journal, January 2006
- Barranco, Manuel; Guardiola, Rafael; Hernández, Susana
- Journal of Low Temperature Physics, Vol. 142, Issue 1-2
Critical Landau Velocity in Helium Nanodroplets
journal, October 2013
- Brauer, Nils B.; Smolarek, Szymon; Loginov, Evgeniy
- Physical Review Letters, Vol. 111, Issue 15
Discrete Visible Luminescence of Helium Atoms and Molecules Desorbing from Helium Clusters: The Role of Electronic, Vibrational, and Rotational Energy Transfer
journal, June 1997
- von Haeften, K.; de Castro, A. R. B.; Joppien, M.
- Physical Review Letters, Vol. 78, Issue 23
Velocity map imaging of ions and electrons using electrostatic lenses: Application in photoelectron and photofragment ion imaging of molecular oxygen
journal, September 1997
- Eppink, André T. J. B.; Parker, David H.
- Review of Scientific Instruments, Vol. 68, Issue 9
Quantum dynamics of Rb atoms desorbing off the surface of He nanodroplets
journal, October 2018
- Dozmorov, N. V.; Baklanov, A. V.; von Vangerow, J.
- Physical Review A, Vol. 98, Issue 4
Desorption Dynamics of Heavy Alkali Metal Atoms (Rb, Cs) Off the Surface of Helium Nanodroplets
journal, April 2014
- von Vangerow, J.; Sieg, A.; Stienkemeier, F.
- The Journal of Physical Chemistry A, Vol. 118, Issue 33
Excitation and ionization of 4 He clusters by electrons
journal, December 1991
- Buchenau, H.; Toennies, J. P.; Northby, J. A.
- The Journal of Chemical Physics, Vol. 95, Issue 11
Highly coherent and stable pulses from the FERMI seeded free-electron laser in the extreme ultraviolet
journal, September 2012
- Allaria, E.; Appio, R.; Badano, L.
- Nature Photonics, Vol. 6, Issue 10
Relaxation times measurement in single and multiply excited xenon clusters
journal, May 2018
- Serdobintsev, P. Yu.; Melnikov, A. S.; Pastor, A. A.
- The Journal of Chemical Physics, Vol. 148, Issue 19
Superfluid Helium Droplets: A Uniquely Cold Nanomatrix for Molecules and Molecular Complexes
journal, May 2004
- Toennies, J. Peter; Vilesov, Andrey F.
- Angewandte Chemie International Edition, Vol. 43, Issue 20
A direct interrogation of superfluidity on molecular scales
journal, July 2002
- Benderskii, A. V.; Eloranta, J.; Zadoyan, R.
- The Journal of Chemical Physics, Vol. 117, Issue 3
Real-Time Dynamics of the Formation of Hydrated Electrons upon Irradiation of Water Clusters with Extreme Ultraviolet Light
journal, April 2019
- LaForge, A. C.; Michiels, R.; Bohlen, M.
- Physical Review Letters, Vol. 122, Issue 13
The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors
journal, October 1970
- Boys, S.F.; Bernardi, F.
- Molecular Physics, Vol. 19, Issue 4, p. 553-566
The photoionization of large pure and doped helium droplets
journal, February 1996
- Fröchtenicht, R.; Henne, U.; Toennies, J. P.
- The Journal of Chemical Physics, Vol. 104, Issue 7
Liquid-Helium Configuration around a Metastable Excited Helium Atom
journal, May 1972
- Hansen, J. P.; Pollock, E. L.
- Physical Review A, Vol. 5, Issue 5
Traces of Vortices in Superfluid Helium Droplets
journal, April 2012
- Gomez, Luis F.; Loginov, Evgeny; Vilesov, Andrey F.
- Physical Review Letters, Vol. 108, Issue 15
Bubble Formation and Decay in and Clusters
journal, May 2002
- von Haeften, K.; Laarmann, T.; Wabnitz, H.
- Physical Review Letters, Vol. 88, Issue 23