kth.sePublications
Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Polarization-sensitive IR-pump-x-ray-probe spectroscopy
North China Elect Power Univ, Dept Math & Phys, Beijing 102206, Peoples R China..
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Theoretical Chemistry and Biology. Siberian Fed Univ, Int Res Ctr Spect & Quantum Chem IRC SQC, Krasnoyarsk 660041, Russia..ORCID iD: 0000-0002-4792-9525
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Theoretical Chemistry and Biology. Siberian Fed Univ, Int Res Ctr Spect & Quantum Chem IRC SQC, Krasnoyarsk 660041, Russia..ORCID iD: 0000-0003-1269-8760
Stockholm Univ, AlbaNova Univ Ctr, Dept Phys, SE-10691 Stockholm, Sweden..ORCID iD: 0000-0002-7023-2486
Show others and affiliations
2021 (English)In: Physical Review A: covering atomic, molecular, and optical physics and quantum information, ISSN 2469-9926, E-ISSN 2469-9934, Vol. 103, no 2, article id 022829Article in journal (Refereed) Published
Abstract [en]

X-ray absorption and core-ionization spectra of molecules pumped by two coherent infrared pulses with different polarizations are studied theoretically. We have found a sensitivity of the vibrational profile of x-ray probe spectra to polarizations of the IR and x-ray pulses. This polarization dependence is qualitatively different for x-ray absorption and x-ray photoelectron spectra. Measurements of this polarization dependence allow to select the difference in Franck-Condon distributions from the lowest and pumped vibrational levels of the electronic ground state. The proposed technique is exemplified numerically using x-ray absorption spectra of the pumped CO molecule. We also show that this kind of pump-probe spectroscopy can enable studies of the dynamics of molecular rotation.

Place, publisher, year, edition, pages
American Physical Society (APS) , 2021. Vol. 103, no 2, article id 022829
National Category
Atom and Molecular Physics and Optics
Identifiers
URN: urn:nbn:se:kth:diva-292239DOI: 10.1103/PhysRevA.103.022829ISI: 000621216900006Scopus ID: 2-s2.0-85101747159OAI: oai:DiVA.org:kth-292239DiVA, id: diva2:1540587
Note

QC 20210329

Available from: 2021-03-29 Created: 2021-03-29 Last updated: 2024-03-18Bibliographically approved
In thesis
1. Multidimensional nuclear dynamics studied by resonant X-ray scattering and pump-probe spectroscopy
Open this publication in new window or tab >>Multidimensional nuclear dynamics studied by resonant X-ray scattering and pump-probe spectroscopy
2021 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis is devoted to the theoretical studies of the multidimensional nuclear dynamics in molecules with the help of X-ray and pump-probe spectroscopy. Using an accurate yet computationally cheap mixed approach multimode X-ray absorption spectra (XAS) and resonant inelastic X-ray scattering (RIXS) spectra of water, methanol, and acetic acid were calculated and compared with the available experimental spectra in the gas and liquid phases. Based on a theoretical study of RIXS in a water molecule through the dissociative core-excited state ∣O1s−14a11⟩, the dynamic origin of the splitting of the lone pair RIXS resonance ∣1b1−14a11⟩ was proved. This result also explains the dynamic nature of the splitting of this peak in liquid water. The decisive role of multimode nuclear dynamics in explaining the experimental XAS and RIXS spectra of methanol, as well as the splitting of the lone pair peak, was theoretically substantiated. RIXS anisotropy effects were fully considered and discussed. The role of hydrogen bonds on vibrational RIXS in the gas phase and liquid acetic acid was analyzed. In contrast to the gas phase, the quasi-elastic RIXS of oxygen K-edge of liquid acetic acid does not exhibit a long vibrational progression, which is qualitatively different from water and methanol. We explained this behavior by the unusually strong influence of the hydrogen bond, which changes the character of the intermediate core-excited state. The combined theoretical-experimental study allowed us to obtain information on the local structure and quantum nuclear dynamics in the liquid system. Besides the advanced theory of RIXS, we developed theory for several new pump-probe techniques, where infrared (IR), ultraviolet (UV), or X-ray pump is combined with XAS or X-ray photoemission spectra (XPS) as a probe. Using accurate theoretical simulations for CO molecule, we show strong sensitivity of X-ray spectra to the relative polarization between IR-pulses and X rays, which can be effectively used for extraction of the weak IR-induced signal. In the framework of UV-pump X-ray probe (UVX-PP) spectroscopy for long overlapping pulses, we show the qualitative difference of the UVX-PP spectra vibrational structure from that of RIXS, allowing for a complementary study of the potential energy surfaces of the valence- and coreexcited molecular states. In the scheme utilizing two time-delayed X-ray pulses we show theoretically that the phase modulation of the XAS is shifted with respect to the phase oscillation comb of the X-ray double pulse, reflecting the dynamics of the light interaction with a quantum system.

Abstract [sv]

Denna avhandling ägnas åt teoretiska studier av den flerdimensionella kärndynamiken i molekyler med hjälp av röntgen- och pump-sondspektroskopi. Med hjälp av en noggrann men ändå beräkningsmässigt billig metod, beräknades multimodalt röntgenabsorptionsspektra (XAS) och resonanselastisk röntgenspridning (RIXS), och jämfördes med tillgängliga experimentella spektra i gas- och vätskefas. Baserat på en teoretisk studie av RIXS i en vattenmolekyl med spridning via det dissociativa kärnexciterade tillståndet ∣O1s−14a11⟩, kunde det dynamiska ursprunget för splittringen av RIXS-resonansen ∣1b1−14a11⟩ bevisas. Detta resultat förklarar också den dynamiska karaktären av uppdelningen av denna topp i flytande vatten. Den avgörande rollen för multimodal kärndynamik för att förklara de experimentella XAS- och RIXS-spektra för metanol, liksom splittringen av den ensamma partoppen, var teoretiskt underbyggd. RIXS anisotropieffekter togs hänsyn till och diskuterades i detalj. Rollen av vätebindningar på vibrationell RIXS i gasformig och flytande ättiksyra analyserades. Till skillnad från gasfas uppvisar kvasielastisk RIXS vid syre K-kanten av flytande ättiksyra ingen lång progression av vibrationsexcitationer, vilket skiljer sig kvalitativt från RIXS i vatten och metanol. Vi förklarade detta beteende med det ovanligt starka inflytandet från vätebindningen, som förändrar karaktären hos det mellanliggande innerskalsexciterade tillståndet. Den kombinerat teoretiska experimentella studien gjorde det möjligt för oss att få information om den lokala strukturen och kvantmekanisk kärndynamik i vätskan. Förutom avancerad teori om RIXS utvecklade vi flera nya pump-sondtekniker, där infraröd (IR), ultraviolett (UV) eller röntgenpump kombineras med röntgen- eller röntgenfotoemissionsspektra (XPS) som sond. Med hjälp av exakta teoretiska simuleringar visar kolmonoxidmolekylen att röntgenspektra har stark känslighet för den relativa polarisationen mellan IR-pulser och röntgenstrålar, som effektivt kan användas för extraktion av den svaga IR-inducerade signalen. Inom ramen för UV-pump röntgensond (UVX-PP) spektroskopi för långa överlappande pulser visade vi kvalitativ skillnad mellan vibrationsstrukturen i UVX-PP-spektra och den i RIXS, vilket möjliggör en kompletterande studie av de potentiella energikurvorna i valens- och kärnexciterade molekylära tillstånd. I schemat som använder två tidsfördröjda röntgenpulser visar vi teoretiskt att fasmoduleringen av XASspektra förskjuts med avseende på fasoscillationskammen för en röntgendubbelpuls, vilket återspeglar dynamiken i ljusinteraktionen med ett kvantsystem.

Place, publisher, year, edition, pages
KTH Royal Institute of Technology, 2021. p. 63
Series
TRITA-CBH-FOU ; 2021:20
National Category
Natural Sciences
Research subject
Theoretical Chemistry and Biology
Identifiers
urn:nbn:se:kth:diva-294214 (URN)978-91-7873-865-6 (ISBN)
Public defence
2021-06-10, https://kth-se.zoom.us/j/65981675023, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 2021-05-11

Available from: 2021-05-11 Created: 2021-05-11 Last updated: 2022-06-25Bibliographically approved

Open Access in DiVA

No full text in DiVA

Other links

Publisher's full textScopus

Authority records

Savchenko, ViktoriiaKimberg, VictorOdelius, MichaelGel'mukhanov, Faris

Search in DiVA

By author/editor
Savchenko, ViktoriiaKimberg, VictorOdelius, MichaelGel'mukhanov, Faris
By organisation
Theoretical Chemistry and Biology
In the same journal
Physical Review A: covering atomic, molecular, and optical physics and quantum information
Atom and Molecular Physics and Optics

Search outside of DiVA

GoogleGoogle Scholar

doi
urn-nbn

Altmetric score

doi
urn-nbn
Total: 43 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf