Emelie Ertan, Viktoriia Savchenko, Nina Ignatova, Vinicius Vaz da Cruz, Rafael C. Couto, Sebastian Eckert, Mattis Fondell, Marcus Dantz, Brian Kennedy, Thorsten Schmitt, Annette Pietzsch, Alexander Föhlisch, Michael Odelius, Victor Kimberg
- In this combined theoretical and experimental study we report on an analysis of the resonant inelastic X-ray scattering (RIXS) spectra of gas phase water via the lowest dissociative core-excited state |1s−1O4a11〉. We focus on the spectral feature near the dissociation limit of the electronic ground state. We show that the narrow atomic-like peak consists of the overlapping contribution from the RIXS channels back to the ground state and to the first valence excited state |1b−114a11〉 of the molecule. The spectral feature has signatures of ultrafast dissociation (UFD) in the core-excited state, as we show by means of ab initio calculations and time-dependent nuclear wave packet simulations. We show that the electronically elastic RIXS channel gives substantial contribution to the atomic-like resonance due to the strong bond length dependence of the magnitude and orientation of the transition dipole moment. By studying the RIXS for an excitation energy scan over the core-excited state resonance, we can understand and single out theIn this combined theoretical and experimental study we report on an analysis of the resonant inelastic X-ray scattering (RIXS) spectra of gas phase water via the lowest dissociative core-excited state |1s−1O4a11〉. We focus on the spectral feature near the dissociation limit of the electronic ground state. We show that the narrow atomic-like peak consists of the overlapping contribution from the RIXS channels back to the ground state and to the first valence excited state |1b−114a11〉 of the molecule. The spectral feature has signatures of ultrafast dissociation (UFD) in the core-excited state, as we show by means of ab initio calculations and time-dependent nuclear wave packet simulations. We show that the electronically elastic RIXS channel gives substantial contribution to the atomic-like resonance due to the strong bond length dependence of the magnitude and orientation of the transition dipole moment. By studying the RIXS for an excitation energy scan over the core-excited state resonance, we can understand and single out the molecular and atomic-like contributions in the decay to the lowest valence-excited state. Our study is complemented by a theoretical discussion of RIXS in the case of isotopically substituted water (HDO and D2O) where the nuclear dynamics is significantly affected by the heavier fragments' mass.…
MetadatenAuthor details: | Emelie ErtanORCiD, Viktoriia Savchenko, Nina Ignatova, Vinicius Vaz da CruzORCiD, Rafael C. Couto, Sebastian EckertORCiDGND, Mattis FondellORCiD, Marcus Dantz, Brian Kennedy, Thorsten Schmitt, Annette PietzschORCiD, Alexander FöhlischORCiDGND, Michael OdeliusORCiD, Victor KimbergORCiD |
---|
DOI: | https://doi.org/10.1039/c8cp01807c |
---|
ISSN: | 1463-9076 |
---|
ISSN: | 1463-9084 |
---|
Pubmed ID: | https://pubmed.ncbi.nlm.nih.gov/29770402 |
---|
Title of parent work (English): | Physical chemistry, chemical physics : a journal of European Chemical Societies |
---|
Publisher: | Royal Society of Chemistry |
---|
Place of publishing: | Cambridge |
---|
Publication type: | Article |
---|
Language: | English |
---|
Date of first publication: | 2018/05/04 |
---|
Publication year: | 2018 |
---|
Release date: | 2021/11/19 |
---|
Volume: | 20 |
---|
Issue: | 21 |
---|
Number of pages: | 14 |
---|
First page: | 14384 |
---|
Last Page: | 14397 |
---|
Funding institution: | Swedish Research CouncilSwedish Research Council [2015-03781, 2015-03956, 2015-04510]; Knut and Alice Wallenberg foundationKnut & Alice Wallenberg Foundation [KAW-2013.0020]; Carl Tryggers Stiftelse [CTS KF 17: 9]; Russian Scientific FoundationRussian Science Foundation (RSF) [16-12-10109]; Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq Brazil)National Council for Scientific and Technological Development (CNPq) [234625/2014-7]; ERC-ADG [669531/EDAX]; Horizon EU Framework Programme for Research and Innovation |
---|
Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |
---|
DDC classification: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften |
---|
Peer review: | Referiert |
---|
Publishing method: | Open Access / Hybrid Open-Access |
---|
License (English): | Creative Commons - Namensnennung - Nicht-kommerziell - Weitergabe unter gleichen Bedingungen 3.0 Unported |
---|