REVIEW 2 major objections 5 minor 69 references
An impinging liquid jet plus a gas assist makes continuous surface-attached sheets thin enough for ultrafast grazing-incidence X-ray work.
Reviewed by Pith at T0; open to challenge. T0 means a machine referee read the full paper against a public rubric. the ladder, T0–T4 →
T0 review · grok-4.5
2026-07-10 12:16 UTC pith:MORQNTBC
load-bearing objection Solid methods paper: continuously renewed, surface-attached, gas-thinned liquid sheets with mapped sub-500 nm acetonitrile channels for grazing-incidence X-ray work. the 2 major comments →
Generation and Characterization of Surface-Attached Ultrathin Liquid Sheets for Grazing-Incidence X-ray Scattering
The pith
A machine-rendered reading of the paper's core claim, the machinery that carries it, and where it could break.
Core claim
Oblique impingement of a liquid microjet on a solid substrate produces stable, continuously flowing surface-attached sheets whose usable thickness can be driven into the sub-micrometer regime, and gas-assisted dual-capillary shaping extends that regime to a millimeter-scale sub-500 nm channel for acetonitrile while preserving continuity and temporal stability near the sensor floor.
What carries the argument
The gas-assisted dual-capillary impinging-jet geometry: a liquid microjet creates a surface-attached sheet, and a co-located gas jet is aimed at the thin side-lobe region to stretch an extended ultrathin channel suitable for a grazing-incidence X-ray footprint.
Load-bearing premise
That the confocal height maps, limited to 250 nm vertical readout and built from liquid-air reflections over a silver mirror, report true physical film thickness rather than an instrument-floor or optical artifact near that limit.
What would settle it
An independent thickness measurement on the same gas-thinned acetonitrile channel (for example optical interferometry or absorption) that systematically exceeds the confocal sub-500 nm claim, or a grazing-incidence pump-probe run that fails to achieve the predicted path-length-limited temporal response.
Editorial analysis
A structured set of objections, weighed in public.
Referee Report
Summary. The manuscript reports a platform for generating continuously renewed, surface-attached liquid sheets by oblique microjet impingement on a flat solid substrate, with optional gas-assisted shaping via a dual-capillary nozzle. Systematic thickness maps from chromatic confocal displacement sensing show that sheet morphology depends on incidence angle, jet velocity, and capillary diameter, and that gas assist can produce an extended thin channel whose measured minimum thickness reaches the 250 nm sensor floor for acetonitrile (conservatively reported as a sub-500 nm region over millimeter-scale lengths). Sparse-grid stability measurements give a median temporal standard deviation of 0.176 µm in the region of interest. Section IV then estimates the implications of these geometries for pump–probe temporal resolution and grazing-incidence hard-X-ray footprints, including velocity-matching conditions.
Significance. Preparing a continuously refreshed, surface-attached liquid film that is thin enough to suppress bulk scattering and optical group-delay smearing is a genuine bottleneck for ultrafast solid–liquid interface studies with hard X-rays. The work supplies a practical, recirculating sample-delivery geometry with quantitative morphology maps, explicit operating windows (angle, velocity, droplet avoidance), and a gas-assisted route to sub-micrometer acetonitrile films over lengths comparable to a grazing-incidence XFEL footprint. The parameter sweeps, stability statistics, and transparent instrument-floor caveats are strengths of a methods paper; if the metrology holds, the platform is enabling for time-resolved grazing-incidence scattering and related spectroscopies.
major comments (2)
- [Sec. III.F, Fig. 6] Sec. III.F and Fig. 6(a,c,d): the central sub-500 nm acetonitrile claim is instrument-limited (250 nm readout). The authors correctly flag this and report conservatively, but the load-bearing metrology claim would be substantially stronger with at least one independent thickness cross-check on the gas-thinned channel (e.g., optical interferometry, absorption, or X-ray transmission/attenuation over a known path). Without that, the existence of an extended thin channel is well supported by the maps, while the absolute floor value remains sensor-bound.
- [Sec. II.C, Sec. IV] Sec. II.C and IV: all maps use a protected silver mirror. For the intended GI X-ray application the substrate will typically be a different solid (catalyst, electrode, oxide). Wetting, contact-line pinning, and hydraulic-jump location can change with surface energy and roughness; a short discussion or one comparative map on a more application-relevant surface would better support transferability of the reported operating windows.
minor comments (5)
- [Fig. 1, Sec. III] Fig. 1(b) caption and Sec. III: the “inner capillary rim” assignment is plausible but could briefly cite the inclined-jet literature already listed (e.g., Kate et al., Li et al.) next to the claim so readers can judge the interpretation without hunting.
- [Sec. III.E, Sec. IV] Eqs. (1)–(6) and Sec. IV: define symbols consistently on first use (e.g., α_X, α_L, h, w_z) in one place; some appear only in prose before the equations.
- [Fig. 6] Fig. 6: state explicitly in the caption the liquid and gas capillary IDs, incidence angle, and approximate gas velocity already given in the text, so the figure is self-contained.
- [Sec. II.D] Data-processing paragraph (Sec. II.D): a one-sentence note on whether any refractive-index correction is applied (or why none is needed for free-surface height relative to exposed mirror) would preempt a common reader question about confocal thin-film artifacts.
- [Sec. IV heading] Minor typography: “TIME-RESOL VED” in the Sec. IV heading has a stray space; “ms −1” spacing is inconsistent in places.
Circularity Check
No significant circularity: experimental metrology and parameter sweeps, not a derivation that reduces to its inputs.
full rationale
This is an experimental methods paper whose central claims are direct observations: impinging-jet and gas-assisted dual-capillary geometries produce surface-attached liquid sheets whose thickness maps, stability statistics, and morphology trends are measured with a commercial chromatic confocal sensor under controlled incidence angle, jet velocity, capillary diameter, and gas assist. Dimensionless numbers (Re_j, We_j, Ca_j, Fr_j) are computed from measured mean jet velocity and literature fluid properties via standard definitions, not fitted to force the reported minimum thicknesses. The sub-500 nm acetonitrile claim is explicitly instrument-limited (250 nm readout) and reported conservatively. Section IV timing estimates are transparent geometric and dispersion extrapolations for future XFEL use; they are not required to establish the sample-delivery result and do not feed back into the thickness measurements. Self-citations to prior Natan et al. ultrafast-scattering work provide application context only and are not load-bearing for the generation or metrology claims. No step reduces a claimed prediction or first-principles result to its own inputs by construction.
Axiom & Free-Parameter Ledger
free parameters (2)
- gas upstream pressure / capillary-limited gas velocity =
~25 psi / ~27.4 m/s
- nozzle–surface distance and dual-capillary lateral offset/rotation =
<8 mm; ~300 µm capillary separation, small lateral offset
axioms (3)
- domain assumption Chromatic confocal wavelength-to-distance calibration correctly converts the peak reflected wavelength into absolute height of the liquid–air interface relative to the local substrate plane.
- domain assumption Oblique impinging circular jets produce non-axisymmetric surface-attached sheets terminated by a hydraulic jump whose morphology is governed by incidence angle, velocity, and nozzle diameter (standard free-surface fluid mechanics).
- domain assumption Literature optical group indices of acetonitrile yield the quoted group-delay mismatch (1.1–1.6 fs/µm) used for temporal-resolution estimates.
read the original abstract
Capturing the ultrafast structural dynamics that occur at the solid-liquid interface is key to understanding adsorption, desorption, diffusion, and aggregation processes in catalysis and interfacial chemical reactions. Hard-X-ray scattering in grazing-incidence geometry can, in principle, access interfacial structural changes with angstrom-scale structural sensitivity and ultrafast temporal resolution. However, the long optical paths of the optical pump and hard-X-ray pulses inside the liquid sample pose significant challenges to the temporal resolution, signal-to-noise ratio, and overall stability of such an experimental scheme. Here, we report a method for creating and characterizing ultrathin surface-attached free-flowing liquid sheets, whose submicrometer thickness enables ultrafast temporal resolution and reduces the bulk-liquid scattering contribution. The impinging-jet geometry produces stable micrometer-scale sheets whose morphology depends systematically on incidence angle, jet velocity, and capillary diameter. Gas-assisted shaping using a second capillary further narrows and thins the sheet, producing an extended ultrathin region and reducing the measured minimum thickness below 500~nm for acetonitrile. The resulting platform provides a reproducible, continuously flowing, surface-attached liquid geometry for grazing-incidence scattering experiments.
Figures
Reference graph
Works this paper leans on
-
[1]
Bulletin of the Chemical Society of Japan , volume=
Ultrafast energy transfer dynamics at solid/liquid interfaces as investigated by photothermal spectroscopy , author=. Bulletin of the Chemical Society of Japan , volume=. 2000 , publisher=
work page 2000
-
[2]
Journal of the Optical Society of America B , volume =
Direct measurement of the group-velocity mismatch and derivation of the refractive-index dispersion for a variety of solvents in the ultraviolet , author =. Journal of the Optical Society of America B , volume =. 2005 , doi =
work page 2005
-
[3]
Refractive, dispersive and thermo-optic properties of twelve organic solvents in the visible and near-infrared , author =. Applied Physics B , volume =. 2014 , doi =
work page 2014
-
[4]
Chemical Physics Letters , volume =
Ultrafast electron diffraction: Velocity mismatch and temporal resolution in crossed-beam experiments , author =. Chemical Physics Letters , volume =. 1993 , doi =
work page 1993
-
[5]
Experiments in Fluids , volume =
Experimental study of flow characteristics of an oblique impinging jet , author =. Experiments in Fluids , volume =. 2020 , doi =
work page 2020
-
[6]
Faraday Discussions , volume =
Resolving multiphoton processes with high-order anisotropy ultrafast X-ray scattering , author =. Faraday Discussions , volume =. 2021 , doi =
work page 2021
-
[7]
Real-space inversion and super-resolution of ultrafast scattering , author =. Physical Review A , volume =. 2023 , doi =
work page 2023
-
[8]
Journal of the American Chemical Society , volume =
Characterization of Deformational Isomerization Potential and Interconversion Dynamics with Ultrafast X-ray Solution Scattering , author =. Journal of the American Chemical Society , volume =. 2024 , doi =
work page 2024
-
[9]
Nature Communications , volume =
Real-space observation of the dissociation of a transition metal complex and its concurrent energy redistribution , author =. Nature Communications , volume =. 2025 , doi =
work page 2025
-
[10]
Ultrafast X-ray imaging of coherently controlled molecular dynamics in real space and time , author =. Physical Review A , volume =. 2026 , doi =
work page 2026
-
[11]
Jacob Stamm and Yibo Wang and Arshad Mehmood and Jiří Suchan and Xinxin Cheng and Michael P Minitti and Siqi Cheng and Kirk A Larsen and Ian Gabalski and Yusong Liu and Marcos Dantus and Thomas J A Wolf and Benjamin G Levine and Adi Natan , title =. ChemRxiv , volume =. 2026 , doi =
work page 2026
-
[12]
Journal of the American Chemical Society , volume=
Toward an atomic-scale understanding of electrochemical interface structure and dynamics , author=. Journal of the American Chemical Society , volume=. 2019 , publisher=
work page 2019
-
[13]
Physical Review Materials , volume=
Validating first-principles molecular dynamics calculations of oxide/water interfaces with x-ray reflectivity data , author=. Physical Review Materials , volume=. 2020 , publisher=
work page 2020
-
[14]
Journal of Chemical Theory and Computation , volume=
First-Principles Molecular Dynamics with Potential and Charge Fluctuations Applied to Au (111) in Alkaline Solutions , author=. Journal of Chemical Theory and Computation , volume=. 2025 , publisher=
work page 2025
-
[15]
Using “tender” X-ray ambient pressure X-ray photoelectron spectroscopy as a direct probe of solid-liquid interface , author=. Scientific reports , volume=. 2015 , publisher=
work page 2015
-
[16]
Reviews in Mineralogy and Geochemistry , volume=
X-ray reflectivity as a probe of mineral-fluid interfaces: A user guide , author=. Reviews in Mineralogy and Geochemistry , volume=. 2002 , publisher=
work page 2002
-
[17]
Review of Scientific Instruments , volume=
Probing the solid-liquid interface with tender x rays: A new ambient-pressure x-ray photoelectron spectroscopy endstation at the Swiss Light Source , author=. Review of Scientific Instruments , volume=. 2020 , publisher=
work page 2020
-
[18]
In-situ surface x-ray scattering of metal monolayers adsorbed at solid-liquid interfaces , author=. Proceedings of SPIE , volume=. 1991 , publisher=
work page 1991
-
[19]
In situ x-ray-diffraction and -reflectivity studies of the Au(111)/electrolyte interface: Reconstruction and anion adsorption , author=. Physical Review B , volume=. 1992 , publisher=
work page 1992
-
[20]
In situ and operando X-ray scattering methods in electrochemistry and electrocatalysis , author=. Chemical Reviews , volume=. 2024 , publisher=
work page 2024
-
[21]
Journal of Physics D: Applied Physics , volume=
Near total reflection x-ray photoelectron spectroscopy: Quantifying chemistry at solid/liquid and solid/solid interfaces , author=. Journal of Physics D: Applied Physics , volume=. 2021 , publisher=
work page 2021
-
[22]
Review of Scientific Instruments , volume=
Micrometer-thickness liquid sheet jets flowing in vacuum , author=. Review of Scientific Instruments , volume=. 2017 , publisher=
work page 2017
-
[23]
Nature communications , volume=
Generation and characterization of ultrathin free-flowing liquid sheets , author=. Nature communications , volume=. 2018 , publisher=
work page 2018
-
[24]
Physical Review Fluids , volume=
Device design and flow scaling for liquid sheet jets , author=. Physical Review Fluids , volume=. 2018 , publisher=
work page 2018
-
[25]
Nature communications , volume=
Ultracompact 3D microfluidics for time-resolved structural biology , author=. Nature communications , volume=. 2020 , publisher=
work page 2020
-
[26]
Sub-micron thick liquid sheets produced by isotropically etched glass nozzles , author=. Lab on a Chip , volume=. 2022 , publisher=
work page 2022
-
[27]
Frontiers in Molecular Biosciences , volume=
Delivery of stable ultra-thin liquid sheets in vacuum for biochemical spectroscopy , author=. Frontiers in Molecular Biosciences , volume=. 2022 , publisher=
work page 2022
-
[28]
Liquid heterostructures: Generation of liquid-liquid interfaces in free-flowing liquid sheets , author=. Langmuir , volume=. 2022 , publisher=
work page 2022
-
[29]
Frontiers in Molecular Biosciences , volume=
Microfluidic liquid sheets as large-area targets for high repetition XFELs , author=. Frontiers in Molecular Biosciences , volume=. 2022 , publisher=
work page 2022
-
[30]
Review of Scientific Instruments , volume=
Generation and simple characterization of flat, liquid jets , author=. Review of Scientific Instruments , volume=. 2020 , publisher=
work page 2020
-
[31]
3D-printed sheet jet for stable megahertz liquid sample delivery at X-ray free-electron lasers , author=. IUCrJ , volume=. 2023 , publisher=
work page 2023
-
[32]
Optics Communications , volume=
A new nozzle producing ultrathin liquid sheets for femtosecond pulse dye lasers , author=. Optics Communications , volume=. 1989 , publisher=
work page 1989
-
[33]
Proceedings of the Royal Society of London
Formation of thin flat sheets of water , author=. Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences , volume=. 1960 , publisher=
work page 1960
-
[34]
Thickness distribution in a sheet formed by impinging jets , author=. AIChE Journal , volume=. 1964 , publisher=
work page 1964
-
[35]
Philosophical Transactions of the Royal Society of London
A photographic investigation into the disintegration of liquid sheets , author=. Philosophical Transactions of the Royal Society of London. Series A, Mathematical and Physical Sciences , volume=. 1954 , publisher=
work page 1954
-
[36]
Journal of Fluid Mechanics , volume=
On the collision of laminar jets: Fluid chains and fishbones , author=. Journal of Fluid Mechanics , volume=. 2004 , publisher=
work page 2004
-
[37]
Characteristics of liquid sheets formed by two impinging jets , author=. Physics of Fluids , volume=. 2006 , publisher=
work page 2006
-
[38]
A liquid flatjet system for solution phase soft-x-ray spectroscopy , author=. Structural Dynamics , volume=. 2015 , publisher=
work page 2015
-
[39]
The Journal of Physical Chemistry Letters , volume=
Femtosecond soft-X-ray absorption spectroscopy of liquids with a water-window high-harmonic source , author=. The Journal of Physical Chemistry Letters , volume=. 2020 , publisher=
work page 2020
-
[40]
Liquid-phase mega-electron-volt ultrafast electron diffraction , author=. Structural Dynamics , volume=. 2020 , publisher=
work page 2020
-
[41]
Direct observation of ultrafast hydrogen bond strengthening in liquid water , author=. Nature , volume=. 2021 , publisher=
work page 2021
-
[42]
Observation of the fastest chemical processes in the radiolysis of water , author=. Science , volume=. 2020 , publisher=
work page 2020
-
[43]
Ultrafast X-ray probing of water structure below the homogeneous ice nucleation temperature , author=. Nature , volume=. 2014 , publisher=
work page 2014
-
[44]
Imaging temperature and thickness of thin planar liquid water jets in vacuum , author=. Structural Dynamics , volume=. 2023 , publisher=
work page 2023
-
[45]
Temperature measurements of liquid flat jets in vacuum , author=. Structural Dynamics , volume=. 2022 , publisher=
work page 2022
-
[46]
Journal of Fluid Mechanics , volume=
The radial spread of a liquid jet over a horizontal plane , author=. Journal of Fluid Mechanics , volume=. 1964 , publisher=
work page 1964
-
[47]
Radial spread of a liquid stream on a horizontal plate , author=. Nature , volume=. 1966 , publisher=
work page 1966
-
[48]
Journal of Fluid Mechanics , volume=
The circular hydraulic jump , author=. Journal of Fluid Mechanics , volume=. 1981 , publisher=
work page 1981
-
[49]
Experiments in Fluids , volume=
The hydraulic jump in circular jet impingement and in other thin liquid films , author=. Experiments in Fluids , volume=. 1993 , publisher=
work page 1993
-
[50]
Journal of Fluid Mechanics , volume=
Hydraulic jumps due to oblique impingement of circular liquid jets on a flat horizontal surface , author=. Journal of Fluid Mechanics , volume=. 2007 , publisher=
work page 2007
-
[51]
Water jet rebounds on hydrophobic surfaces: a first step to jet micro-fluidics , author=. Soft Matter , volume=. 2010 , publisher=
work page 2010
-
[52]
Experiments in fluids , volume=
Experimental investigation of inclined liquid water jet flow onto vertically located superhydrophobic surfaces , author=. Experiments in fluids , volume=. 2010 , publisher=
work page 2010
-
[53]
Sigma Journal of Engineering and Natural Sciences , volume=
The spreading profile of an impinging liquid jet on the hydrophobic surfaces , author=. Sigma Journal of Engineering and Natural Sciences , volume=. 2018 , publisher=
work page 2018
-
[54]
Effect of surface contact angle on the wall impingement of a power-law liquid jet , author=. Physics of Fluids , volume=. 2021 , publisher=
work page 2021
-
[55]
Chemical Engineering Science , volume=
Flow in the thin film created by a coherent turbulent water jet impinging on a vertical wall , author=. Chemical Engineering Science , volume=. 2016 , publisher=
work page 2016
-
[56]
Journal of Fluid Mechanics , volume=
On the origin of the circular hydraulic jump in a thin liquid film , author=. Journal of Fluid Mechanics , volume=. 2018 , publisher=
work page 2018
-
[57]
International Journal of Heat and Mass Transfer , volume=
Heat transfer and hydrodynamics of free water jet impingement at low nozzle-to-plate spacings , author=. International Journal of Heat and Mass Transfer , volume=. 2017 , publisher=
work page 2017
-
[58]
Journal of Fluid Mechanics , volume=
The influence of surface tension on the circular hydraulic jump , author=. Journal of Fluid Mechanics , volume=. 2003 , publisher=
work page 2003
-
[59]
Physical review letters , volume=
Drop splashing on a dry smooth surface , author=. Physical review letters , volume=. 2005 , publisher=
work page 2005
-
[60]
Physical Review Letters , volume=
Generation of steady liquid microthreads and micron-sized monodisperse sprays in gas streams , author=. Physical Review Letters , volume=. 1998 , publisher=
work page 1998
-
[61]
Journal of Physics D: Applied Physics , volume=
Gas dynamic virtual nozzle for generation of microscopic droplet streams , author=. Journal of Physics D: Applied Physics , volume=. 2008 , publisher=
work page 2008
-
[62]
Three-dimensional-printed gas dynamic virtual nozzles for x-ray laser sample delivery , author=. Optics Express , volume=. 2016 , publisher=
work page 2016
-
[63]
International Journal of Multiphase Flow , volume=
Computational modeling and simulation of gas focused liquid micro-sheets , author=. International Journal of Multiphase Flow , volume=. 2021 , publisher=
work page 2021
-
[64]
Progress in Computational Fluid Dynamics, An International Journal , volume=
A numerical study on the influence of liquid properties on gas-focused micro-jets , author=. Progress in Computational Fluid Dynamics, An International Journal , volume=. 2020 , publisher=
work page 2020
-
[65]
International Journal of Multiphase Flow , volume=
Influence of gas dynamic virtual nozzle geometry on micro-jet characteristics , author=. International Journal of Multiphase Flow , volume=. 2018 , publisher=
work page 2018
-
[66]
Emergence and dynamics of gas-accelerated liquid sheets: Insights into liquid chain formation , author=. Physics of Fluids , volume=. 2026 , publisher=
work page 2026
-
[67]
High-precision chromatic confocal technologies: a review , author=. Micromachines , volume=. 2024 , publisher=
work page 2024
-
[68]
Thickness measurement method for self-supporting film with double chromatic confocal probes , author=. Applied Optics , volume=. 2021 , publisher=
work page 2021
-
[69]
Nanomanufacturing and Metrology , volume=
A new method for measuring multilayer thickness using a chromatic confocal sensor , author=. Nanomanufacturing and Metrology , volume=. 2024 , publisher=
work page 2024
discussion (0)
Sign in with ORCID, Apple, or X to comment. Anyone can read and Pith papers without signing in.