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Title: 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:
ORCiD logo [1]; ORCiD logo [2];  [3];  [4]; ORCiD logo [5];  [4];  [5]; ORCiD logo [6]; ORCiD logo [5]; ORCiD logo [7];  [5]; ORCiD logo [8]; ORCiD logo [9];  [10]; ORCiD logo [11];  [12];  [13];  [5];  [5]; ORCiD logo [5] more »;  [11];  [14];  [15]; ORCiD logo [16]; ORCiD logo [17]; ORCiD logo [18] « less
+ Show Author Affiliations
  1. Aarhus Univ. (Denmark)
  2. Univ. of Freiburg, Freiburg im Breisgau (Germany); Univ. of Connecticut, Storrs, CT (United States)
  3. Central European Research Infrastructure Consortium (CERIC–ERIC), Trieste (Italy); Italian National Research Council (CNR), Monterotondo Scalo (Italy)
  4. Italian National Research Council (CNR), Monterotondo Scalo (Italy)
  5. Elettra Sincrotrone Trieste (Italy)
  6. Italian National Research Council (CNR), Trieste (Italy); Univ. degli Studi, Milan (Italy)
  7. Ecole Polytechnique Fédérale de Lausanne (EPFL), Lausanne (Switzerland)
  8. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  9. Italian National Research Council (CNR), Trieste (Italy)
  10. Kido Dynamics, Lausanne (Switzerland); Inst. de Fisica Interdisciplinar y Sistemas Complejos, Palma de Mallorca (Spain)
  11. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  12. European X-Ray Free-Electron Laser Facility (XFEL), Schenefeld (Germany); Inst. für Optik und Atomare Physik, Berlin (Germany)
  13. Univ. degli Studi, Milan (Italy)
  14. Inst. für Optik und Atomare Physik, Berlin (Germany)
  15. California State Univ., Northridge, CA (United States)
  16. Univ. de Barcelona (Spain)
  17. Univ. de Barcelona (Spain); Univ. Paul Sabatier-Toulouse (France)
  18. 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.
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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
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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.
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@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}
}
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Works referenced in this record:

Electronic excitations in liquid helium: The evolution from small clusters to large droplets
journal, October 1993

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
  • DOI: 10.1021/acs.jpclett.6b02598

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
  • DOI: 10.1038/nature08811

Interaction of Helium Rydberg State Atoms with Superfluid Helium
journal, December 2013

Three-Dimensional Shapes of Spinning Helium Nanodroplets
journal, December 2018

Laser-Induced Rotation of Iodine Molecules in Helium Nanodroplets: Revivals and Breaking Free
journal, May 2017

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
  • DOI: 10.1063/1.1835953

Nature of the excited states of He 2
journal, October 1975

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
  • DOI: 10.1002/wcms.82

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
  • DOI: 10.1088/0953-4075/39/8/R01

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
  • DOI: 10.1039/c3cp52221k

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
  • DOI: 10.1063/1.4768422

Desorption of alkali atoms from 4He nanodroplets
journal, January 2012

  • Hernando, Alberto; Barranco, Manuel; Pi, Martí
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 11
  • DOI: 10.1039/c2cp23526a

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
  • DOI: 10.1007/BF01117405

Femtosecond photoexcitation dynamics inside a quantum solvent
journal, October 2018

Rapidly pulsed helium droplet source
journal, April 2009

  • Pentlehner, Dominik; Riechers, Ricarda; Dick, Bernhard
  • Review of Scientific Instruments, Vol. 80, Issue 4
  • DOI: 10.1063/1.3117196

Coupled Electronic and Structural Relaxation Pathways in the Postexcitation Dynamics of Rydberg States of BaAr N Clusters
journal, September 2014

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
  • DOI: 10.1063/1.4972258

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
  • DOI: 10.1063/1.455993

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
  • DOI: 10.1063/1.1807578

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
  • DOI: 10.1063/1.4900503

Electronic excitation, decay and photochemical processes in rare gas clusters
journal, January 1995

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
  • DOI: 10.1088/0953-4075/46/16/164007

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
  • DOI: 10.1021/jp2004216

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
  • DOI: 10.1063/1.473322

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
  • DOI: 10.1039/c0cp02355h

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
  • DOI: 10.1038/nature12936

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
  • DOI: 10.1073/pnas.1014982107

Photoelectron Imaging of Helium Droplets
journal, July 2003

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
  • DOI: 10.1063/1.4869193

Coherent diffractive imaging of single helium nanodroplets with a high harmonic generation source
journal, September 2017

Heterogeneous Photochemistry in the Atmosphere
journal, February 2015

  • George, Christian; Ammann, Markus; D’Anna, Barbara
  • Chemical Reviews, Vol. 115, Issue 10
  • DOI: 10.1021/cr500648z

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
  • DOI: 10.1021/ja310596a

Dynamics of the Formation of an Electron Bubble in Liquid Helium
journal, November 1995

Helium Nanodroplets: An Overview
journal, January 2006

  • Barranco, Manuel; Guardiola, Rafael; Hernández, Susana
  • Journal of Low Temperature Physics, Vol. 142, Issue 1-2
  • DOI: 10.1007/s10909-005-9267-0

Critical Landau Velocity in Helium Nanodroplets
journal, October 2013

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
  • DOI: 10.1063/1.1148310

Quantum dynamics of Rb atoms desorbing off the surface of He nanodroplets
journal, October 2018

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
  • DOI: 10.1021/jp503308w

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
  • DOI: 10.1063/1.461294

Highly coherent and stable pulses from the FERMI seeded free-electron laser in the extreme ultraviolet
journal, September 2012

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
  • DOI: 10.1063/1.5025274

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
  • DOI: 10.1002/anie.200300611

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
  • DOI: 10.1063/1.1485955

Real-Time Dynamics of the Formation of Hydrated Electrons upon Irradiation of Water Clusters with Extreme Ultraviolet Light
journal, April 2019

The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors
journal, October 1970

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
  • DOI: 10.1063/1.471009

Liquid-Helium Configuration around a Metastable Excited Helium Atom
journal, May 1972

Traces of Vortices in Superfluid Helium Droplets
journal, April 2012

Bubble Formation and Decay in H 3 e and H 4 e Clusters
journal, May 2002

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