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One-dimensional cuts through multidimensional potential-energy surfaces by tunable x rays

Sebastian Eckert, Vinícius Vaz da Cruz, Faris Gel'mukhanov, Emelie Ertan, Nina Ignatova, Sergey Polyutov, Rafael C. Couto, Mattis Fondell, Marcus Dantz, Brian Kennedy, Thorsten Schmitt, Annette Pietzsch, Michael Odelius, and Alexander Föhlisch
Phys. Rev. A 97, 053410 – Published 18 May 2018

Abstract

The concept of the potential-energy surface (PES) and directional reaction coordinates is the backbone of our description of chemical reaction mechanisms. Although the eigenenergies of the nuclear Hamiltonian uniquely link a PES to its spectrum, this information is in general experimentally inaccessible in large polyatomic systems. This is due to (near) degenerate rovibrational levels across the parameter space of all degrees of freedom, which effectively forms a pseudospectrum given by the centers of gravity of groups of close-lying vibrational levels. We show here that resonant inelastic x-ray scattering (RIXS) constitutes an ideal probe for revealing one-dimensional cuts through the ground-state PES of molecular systems, even far away from the equilibrium geometry, where the independent-mode picture is broken. We strictly link the center of gravity of close-lying vibrational peaks in RIXS to a pseudospectrum which is shown to coincide with the eigenvalues of an effective one-dimensional Hamiltonian along the propagation coordinate of the core-excited wave packet. This concept, combined with directional and site selectivity of the core-excited states, allows us to experimentally extract cuts through the ground-state PES along three complementary directions for the showcase H2O molecule.

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  • Received 23 January 2018

DOI:https://doi.org/10.1103/PhysRevA.97.053410

Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI.

Published by the American Physical Society

Physics Subject Headings (PhySH)

Atomic, Molecular & Optical

Authors & Affiliations

Sebastian Eckert1,2,*, Vinícius Vaz da Cruz3,†, Faris Gel'mukhanov3,4, Emelie Ertan5, Nina Ignatova3,4, Sergey Polyutov4, Rafael C. Couto3, Mattis Fondell2, Marcus Dantz6, Brian Kennedy2, Thorsten Schmitt6, Annette Pietzsch2, Michael Odelius5,‡, and Alexander Föhlisch1,2

  • 1Institut für Physik und Astronomie, Universität Potsdam, Karl-Liebknecht-Strasse 24-25, 14476 Potsdam, Germany
  • 2Institute for Methods and Instrumentation for Synchrotron Radiation Research FG-ISRR, Helmholtz-Zentrum Berlin für Materialien und Energie, Albert-Einstein-Strasse 15, 12489 Berlin, Germany
  • 3Theoretical Chemistry and Biology, Royal Institute of Technology, 10691 Stockholm, Sweden
  • 4Institute of Nanotechnology, Spectroscopy, and Quantum Chemistry, Siberian Federal University, 660041 Krasnoyarsk, Russia
  • 5Department of Physics, Stockholm University, AlbaNova University Center, 10691 Stockholm, Sweden
  • 6Research Department Synchrotron Radiation and Nanotechnology, Paul Scherrer Institut, CH-5232 Villigen PSI, Switzerland

  • *sebeckert@uni-potsdam.de
  • vvdc@kth.se
  • odelius@fysik.su.se

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Issue

Vol. 97, Iss. 5 — May 2018

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