Infrared-pump–x-ray-probe spectroscopy of vibrationally excited molecules

Nina Ignatova, Vinícius V. da Cruz, Rafael C. Couto, Emilie Ertan, Michael Odelius, Hans Ågren, Freddy F. Guimarães, Andrei Zimin, Sergey P. Polyutov, Faris Gel'mukhanov, and Victor Kimberg
Phys. Rev. A 95, 042502 – Published 7 April 2017

Abstract

We develop a theory of infrared (IR)-pump–x-ray-probe spectroscopy for molecular studies. We illustrate advantages of the proposed scheme by means of numerical simulations employing a vibrational wave packet technique applied to x-ray absorption and resonant inelastic x-ray scattering (RIXS) spectra of the water molecule vibrationally excited by a preceding IR field. The promotion of the vibrationally excited molecule to the dissociative 1a114a1 and bound 1a112b2 core-excited states with qualitatively different shapes of the potential energy surfaces creates nuclear wave packets localized along and between the OH bonds, respectively. The projection of these wave packets on the final vibrational states, governed by selection and propensity rules, results in spatial selectivity of RIXS sensitive to the initial vibrationally excited state, which makes it possible to probe selectively the ground state properties along different modes. In addition, we propose to use RIXS as a tool to study x-ray absorption from a selected vibrational level of the ground state when the spectral resolution is sufficiently high to resolve vibrational overtones. The proposed technique has potential applications for advanced mapping of multidimensional potential energy surfaces of ground and core-excited molecular states, for symmetry-resolved spectroscopy, and for steering chemical reactions.

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  • Received 12 October 2016
  • Revised 6 February 2017

DOI:https://doi.org/10.1103/PhysRevA.95.042502

©2017 American Physical Society

Physics Subject Headings (PhySH)

Atomic, Molecular & Optical

Authors & Affiliations

Nina Ignatova1,2,*, Vinícius V. da Cruz2, Rafael C. Couto2,3, Emilie Ertan4, Michael Odelius4, Hans Ågren1,2, Freddy F. Guimarães3, Andrei Zimin1,2, Sergey P. Polyutov1, Faris Gel'mukhanov1,2, and Victor Kimberg1,2,†

  • 1Institute of Nanotechnology, Spectroscopy and Quantum Chemistry, Siberian Federal University, 660041 Krasnoyarsk, Russia
  • 2Theoretical Chemistry and Biology, Royal Institute of Technology, 10691 Stockholm, Sweden
  • 3Instituto de Química, Universidade Federal de Goiás, Campus Samambaia, CP 131 CEP 74001-970, Goiânia-GO, Brazil
  • 4Department of Physics, Stockholm University, AlbaNova University Center, 10691 Stockholm, Sweden

  • *ninai@kth.se
  • kimberg@kth.se

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Issue

Vol. 95, Iss. 4 — April 2017

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