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da Cruz, Vinicius Vaz
Publications (8 of 8) Show all publications
Niskanen, J., Fondell, M., Sahle, C. J., Eckert, S., Jay, R. M., Gilmore, K., . . . Foehlisch, A. (2019). Compatibility of quantitative X-ray spectroscopy with continuous distribution models of water at ambient conditions. Proceedings of the National Academy of Sciences of the United States of America, 116(10), 4058-4063
Open this publication in new window or tab >>Compatibility of quantitative X-ray spectroscopy with continuous distribution models of water at ambient conditions
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2019 (English)In: Proceedings of the National Academy of Sciences of the United States of America, ISSN 0027-8424, E-ISSN 1091-6490, Vol. 116, no 10, p. 4058-4063Article in journal (Refereed) Published
Abstract [en]

The phase diagram of water harbors controversial views on underlying structural properties of its constituting molecular moieties, its fluctuating hydrogen-bonding network, as well as pair-correlation functions. In this work, long energy-range detection of the X-ray absorption allows us to unambiguously calibrate the spectra for water gas, liquid, and ice by the experimental atomic ionization cross-section. In liquid water, we extract the mean value of 1.74 +/- 2.1% donated and accepted hydrogen bonds per molecule, pointing to a continuous-distribution model. In addition, resonant inelastic X-ray scattering with unprecedented energy resolution also supports continuous distribution of molecular neighborhoods within liquid water, as do X-ray emission spectra once the femtosecond scattering duration and proton dynamics in resonant X-ray-matter interaction are taken into account. Thus, X-ray spectra of liquid water in ambient conditions can be understood without a two-structure model, whereas the occurrence of nanoscale-length correlations within the continuous distribution remains open.

Place, publisher, year, edition, pages
NATL ACAD SCIENCES, 2019
Keywords
structure of water, X-ray spectroscopy, continuous distribution model
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-247814 (URN)10.1073/pnas.1815701116 (DOI)000460242100026 ()30782822 (PubMedID)2-s2.0-85062462267 (Scopus ID)
Note

QC 20190327

Available from: 2019-03-27 Created: 2019-03-27 Last updated: 2019-05-16Bibliographically approved
da Cruz, V. V., Ignatova, N., Couto, R. C., Fedotov, D. A., Rehn, D. R., Savchenko, V., . . . Kimberg, V. (2019). Nuclear dynamics in resonant inelastic X-ray scattering and X-ray absorption of methanol. Journal of Chemical Physics, 150(23), Article ID 234301.
Open this publication in new window or tab >>Nuclear dynamics in resonant inelastic X-ray scattering and X-ray absorption of methanol
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2019 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 150, no 23, article id 234301Article in journal (Refereed) Published
Abstract [en]

We report on a combined theoretical and experimental study of core-excitation spectra of gas and liquid phase methanol as obtained with the use of X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS). The electronic transitions are studied with computational methods that include strict and extended second-order algebraic diagrammatic construction [ADC(2) and ADC(2)-x], restricted active space second-order perturbation theory, and time-dependent density functional theory-providing a complete assignment of the near oxygen K-edge XAS. We show that multimode nuclear dynamics is of crucial importance for explaining the available experimental XAS and RIXS spectra. The multimode nuclear motion was considered in a recently developed "mixed representation" where dissociative states and highly excited vibrational modes are accurately treated with a time-dependent wave packet technique, while the remaining active vibrational modes are described using Franck-Condon amplitudes. Particular attention is paid to the polarization dependence of RIXS and the effects of the isotopic substitution on the RIXS profile in the case of dissociative core-excited states. Our approach predicts the splitting of the 2a RIXS peak to be due to an interplay between molecular and pseudo-atomic features arising in the course of transitions between dissociative core- and valence-excited states. The dynamical nature of the splitting of the 2a peak in RIXS of liquid methanol near pre-edge core excitation is shown. The theoretical results are in good agreement with our liquid phase measurements and gas phase experimental data available from the literature.

Place, publisher, year, edition, pages
American Institute of Physics (AIP), 2019
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-255315 (URN)10.1063/1.5092174 (DOI)000472600300006 ()31228920 (PubMedID)2-s2.0-85067465364 (Scopus ID)
Note

QC 20190807

Available from: 2019-08-07 Created: 2019-08-07 Last updated: 2019-08-07Bibliographically approved
da Cruz, V. V., Gel'mukhanov, F., Eckert, S., Iannuzzi, M., Ertan, E., Pietzsch, A., . . . Odelius, M. (2019). Probing hydrogen bond strength in liquid water by resonant inelastic X-ray scattering. Nature Communications, 10, Article ID 1013.
Open this publication in new window or tab >>Probing hydrogen bond strength in liquid water by resonant inelastic X-ray scattering
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2019 (English)In: Nature Communications, ISSN 2041-1723, E-ISSN 2041-1723, Vol. 10, article id 1013Article in journal (Refereed) Published
Abstract [en]

Local probes of the electronic ground state are essential for understanding hydrogen bonding in aqueous environments. When tuned to the dissociative core-excited state at the O1s pre-edge of water, resonant inelastic X-ray scattering back to the electronic ground state exhibits a long vibrational progression due to ultrafast nuclear dynamics. We show how the coherent evolution of the OH bonds around the core-excited oxygen provides access to high vibrational levels in liquid water. The OH bonds stretch into the long-range part of the potential energy curve, which makes the X-ray probe more sensitive than infra-red spectroscopy to the local environment. We exploit this property to effectively probe hydrogen bond strength via the distribution of intramolecular OH potentials derived from measurements. In contrast, the dynamical splitting in the spectral feature of the lowest valence-excited state arises from the short-range part of the OH potential curve and is rather insensitive to hydrogen bonding.

Place, publisher, year, edition, pages
NATURE PUBLISHING GROUP, 2019
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-246231 (URN)10.1038/s41467-019-08979-4 (DOI)000460125000002 ()30833573 (PubMedID)2-s2.0-85062425511 (Scopus ID)
Note

QC 20190403

Available from: 2019-04-03 Created: 2019-04-03 Last updated: 2019-04-03Bibliographically approved
Ceolin, D., Liu, J.-C., da Cruz, V. V., Ågren, H., Journel, L., Guillemin, R., . . . Gel'mukhanov, F. (2019). Recoil-induced ultrafast molecular rotation probed by dynamical rotational Doppler effect. Proceedings of the National Academy of Sciences of the United States of America, 116(11), 4877-4882
Open this publication in new window or tab >>Recoil-induced ultrafast molecular rotation probed by dynamical rotational Doppler effect
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2019 (English)In: Proceedings of the National Academy of Sciences of the United States of America, ISSN 0027-8424, E-ISSN 1091-6490, Vol. 116, no 11, p. 4877-4882Article in journal (Refereed) Published
Abstract [en]

Observing and controlling molecular motion and in particular rotation are fundamental topics in physics and chemistry. To initiate ultrafast rotation, one needs a way to transfer a large angular momentum to the molecule. As a showcase, this was performed by hard X-ray C1s ionization of carbon monoxide accompanied by spinning up the molecule via the recoil "kick" of the emitted fast photoelectron. To visualize this molecular motion, we use the dynamical rotational Doppler effect and an X-ray "pump-probe" device offered by nature itself: the recoil-induced ultrafast rotation is probed by subsequent Auger electron emission. The time information in our experiment originates from the natural delay between the C1s photoionization initiating the rotation and the ejection of the Auger electron. From a more general point of view, time-resolved measurements can be performed in two ways: either to vary the "delay" time as in conventional time-resolved pump-probe spectroscopy and use the dynamics given by the system, or to keep constant delay time and manipulate the dynamics. Since in our experiment we cannot change the delay time given by the core-hole lifetime tau, we use the second option and control the rotational speed by changing the kinetic energy of the photoelectron. The recoil-induced rotational dynamics controlled in such a way is observed as a photon energy-dependent asymmetry of the Auger line shape, in full agreement with theory. This asymmetry is explained by a significant change of the molecular orientation during the core-hole lifetime, which is comparable with the rotational period.

Place, publisher, year, edition, pages
NATL ACAD SCIENCES, 2019
Keywords
rotational Doppler effect, recoil effect, ultrafast rotation, hard X-ray, Auger peak asymmetry
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-247807 (URN)10.1073/pnas.1807812116 (DOI)000460911500027 ()30733297 (PubMedID)2-s2.0-85062818673 (Scopus ID)
Note

QC 20190401

Available from: 2019-04-01 Created: 2019-04-01 Last updated: 2019-04-01Bibliographically approved
Niskanen, J., Fondell, M., Sahle, C. J., Eckert, S., Jay, R. M., Gilmore, K., . . . Foehlisch, A. (2019). REPLY TO PETTERSSON ET AL.: Why X-ray spectral features are compatible to continuous distribution models in ambient water [Letter to the editor]. Proceedings of the National Academy of Sciences of the United States of America, 116(35), 17158-17159
Open this publication in new window or tab >>REPLY TO PETTERSSON ET AL.: Why X-ray spectral features are compatible to continuous distribution models in ambient water
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2019 (English)In: Proceedings of the National Academy of Sciences of the United States of America, ISSN 0027-8424, E-ISSN 1091-6490, Vol. 116, no 35, p. 17158-17159Article in journal, Letter (Refereed) Published
Place, publisher, year, edition, pages
NATL ACAD SCIENCES, 2019
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-259440 (URN)10.1073/pnas.1909551116 (DOI)000483396800007 ()31431526 (PubMedID)2-s2.0-85071402351 (Scopus ID)
Note

QC 20190923

Available from: 2019-09-23 Created: 2019-09-23 Last updated: 2019-09-23Bibliographically approved
da Cruz, V. V., Ertan, E., Ignatova, N., Couto, R. C., Polyutov, S., Odelius, M., . . . Gel'mukhanov, F. (2018). Anomalous polarization dependence in vibrationally resolved resonant inelastic x-ray scattering of H2O. Physical Review A: covering atomic, molecular, and optical physics and quantum information, 98(1), Article ID 012507.
Open this publication in new window or tab >>Anomalous polarization dependence in vibrationally resolved resonant inelastic x-ray scattering of H2O
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2018 (English)In: Physical Review A: covering atomic, molecular, and optical physics and quantum information, ISSN 2469-9926, E-ISSN 2469-9934, Vol. 98, no 1, article id 012507Article in journal (Refereed) Published
Abstract [en]

It is well established that different electronic channels, in resonant inelastic x-ray scattering (RIXS), display different polarization dependences due to different orientations of their corresponding transition dipole moments in the molecular frame. However, this effect does not influence the vibrational progression in the Franck-Condon approximation. We have found that the transition dipole moments of core excitation and deexcitation experience ultrafast rotation during dissociation in the intermediate core-excited state. This rotation makes the vibrational progression in RIXS sensitive to the polarization of the x-ray photons. We study the water molecule, in which the effect is expressed in RIXS through the dissociative core-excited state where the vibrational scattering anisotropy is accompanied also by violation of parity selection rules for the vibrations.

Place, publisher, year, edition, pages
American Physical Society, 2018
National Category
Physical Sciences
Identifiers
urn:nbn:se:kth:diva-232763 (URN)10.1103/PhysRevA.98.012507 (DOI)000439279500006 ()2-s2.0-85050471678 (Scopus ID)
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation, KAW-2013.0020Carl Tryggers foundation
Note

QC 20180803

Available from: 2018-08-03 Created: 2018-08-03 Last updated: 2018-08-06Bibliographically approved
Eckert, S., da Cruz, V. V., Gel'mukhanov, F., Ertan, E., Ignatova, N., Polyutov, S., . . . Foehlisch, A. (2018). One-dimensional cuts through multidimensional potential-energy surfaces by tunable x rays. Physical Review A: covering atomic, molecular, and optical physics and quantum information, 97(5), Article ID 053410.
Open this publication in new window or tab >>One-dimensional cuts through multidimensional potential-energy surfaces by tunable x rays
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2018 (English)In: Physical Review A: covering atomic, molecular, and optical physics and quantum information, ISSN 2469-9926, E-ISSN 2469-9934, Vol. 97, no 5, article id 053410Article in journal (Refereed) Published
Abstract [en]

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.

Place, publisher, year, edition, pages
AMER PHYSICAL SOC, 2018
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-230442 (URN)10.1103/PhysRevA.97.053410 (DOI)000433002600009 ()2-s2.0-85047724572 (Scopus ID)
Note

QC 20180614

Available from: 2018-06-14 Created: 2018-06-14 Last updated: 2018-06-14Bibliographically approved
Ertan, E., Savchenko, V., Ignatova, N., da Cruz, V. V., Couto, R. C., Eckert, S., . . . Kimberg, V. (2018). Ultrafast dissociation features in RIXS spectra of the water molecule. Physical Chemistry, Chemical Physics - PCCP
Open this publication in new window or tab >>Ultrafast dissociation features in RIXS spectra of the water molecule
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2018 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084Article in journal (Refereed) Published
Abstract [en]

In this combined theoretical and experimental study we report on an analysis of the resonant inelastic X-ray scattering spectra (RIXS) of gas phase water via the lowest dissociative core-excited state |1sO-14a11〉. 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 |1b1-14a11〉 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 the isotope substituted water (HDO and D2O) where the nuclear dynamics is significantly affected by the heavier fragments' mass.

Keywords
resonant inelastic X-ray scattering, water molecule, Ultrafast dissociation, valence excited state, core-excited state
National Category
Atom and Molecular Physics and Optics
Research subject
Chemistry; Physics
Identifiers
urn:nbn:se:kth:diva-227942 (URN)10.1039/C8CP01807C (DOI)000434246300010 ()2-s2.0-85048446772 (Scopus ID)
Note

QC 20180516

Available from: 2018-05-15 Created: 2018-05-15 Last updated: 2019-08-27Bibliographically approved
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