dataesr/scientific-paragraphs-categorization huggingface dataset:
The timestamp of the proton bunches impinging into the target of ISOLDE was also recorded and used to define the time gates in the data analysis. Laser system: A three-step resonance ionization scheme was used in this experiment. The laser light for the first excitation step was produced by a continuous wave (cw) titanium-sapphire (Ti:Sa) laser (M-Squared SolsTiS) pumped by an 18-W laser at 532 nm (Lighthouse Photonics). In order to avoid optical pumping to dark states due to long interaction times, this cw light was "chopped" into 50-ns pulses at a repetition rate of 100 Hz by using a Pockels cell  [20]. The wavelength of this narrowband laser was tuned to probe the hfs of the 4s 2 S 1/2 → 4p 2 P 1/2 transition at 769 nm. Atoms in the excited 4p 2 P 1/2 state were subsequently further excited to the 6s 2 S 1/2 atomic state by a pulsed dye laser (Spectron PDL SL4000) with a spectral bandwidth of 10 GHz.
Charge radii extraction: The perturbation of the atomic states caused by the different nuclear charge distribution in isotopes leads to small differences in the atomic transition frequency, δν AA , between centroids (ν A ,ν A ) of the hfs of two isotopes with mass number A and A. The isotope shifts of 48-52 K were extracted from the hfs spectra of 47-52 K analyzed using the SATLAS  [32]  Python package, as displayed in third column of Table  II , along with all available results from literature. More details on the analysis process can be found in Ref. [21]. The changes in the nuclear mean-square charge radii of 36-52 K can then be extracted from the isotope shifts using: δν AA = K MS m A -m A m A (m A + m e ) + F δ r 2 AA , (2) where K MS and F are the atomic mass shift and field shift, m stands for the nuclear mass of isotopes A, A , and an electron.
Acknowledgments We acknowledge the support of the ISOLDE collaboration and technical teams. This work was supported in part by the  National Key R&D Program of China  (Contract No:  2018YFA0404403 ); the  National Natural Science Foundation of China  (No: 11875073 ); the  BriX Research Program  No. P7/12 ,  FWO-Vlaanderen (Belgium) ,  GOA 15/010  from  KU Leuven ;  ERC Consolidator Grant  no. 648381  (FNPMLS); the  STFC  consolidated grants  ST/L005794/1  and  ST/L005786/1  and  Ernest Rutherford Grant  No. ST/L002868/1 ; the  EU   Horizon2020 research and innovation programme  through  ENSAR2  (no. 654002 ); the  U. S. Department of Energy, Office of Science, Office of Nuclear Physics  under grants  DE-00249237 ,  DE-FG02-96ER40963  and  DE-SC0018223  (SciDAC-4 NUCLEI collaboration). This work received funding from the  European Research Council (ERC)  under the European Union's  Horizon 2020 research and innovation programme  (Grant agreement No.
3 and 19. 3 Å (Figure  2a, b ). The main structural differences associated to the incorporation of TZDC are reflected on changes to the coordination bonds. The Zr-µ3O and Zr-µ2O distances in the metal-oxo cluster and the carboxylate group are elongated up to 0. 012 Å in UiO-68-TZDC due to the electron withdrawing nature of the tetrazine core (Table  S2 ). As for the internal structure of the linkers, the carboxylate groups remain coplanar in both cases but the central ring presents a certain degree of disorder. We collected crystallographic data at room temperature (UiO-68-TZDC) and 100 K (UiO-68). The disorder is present in both cases which suggests this is intrinsic to the crystallographic packing of the solids and not thermal in origin. The effect of the tetrazine core is more notable in the thermal and chemical stability of the frameworks.
ACKNOWLEDGMENT This work was supported by the  EU (ERC Stg Chem -fs-MOF 714122) and  Spanish government  ( CTQ2017-83486-P ,  RTI2018-098568-A-I00 & CEX2019-000919-M ). B. L. -B. thanks the  Spanish government for a FPU  ( FPU16/04162 ). N. M. P. thanks the  European Union  for a  Marie Skłodowska-Curie Global Fellowship  ( H2020-MSCA-IF-2016-GF-749359-EnanSET ). JGP thanks to the  SIDIX at Servicios Generales de Apoyo a la Investigación (SEGAI) at La Laguna University.
These observations included 12 CO and 13 CO and aim to estimate how common substructures are around VLMS. In addition, as radial drift is expected to be very efficient in these disks, they are excellent laboratories to search for the difference between the radial extent of the gas and dust in disks, which can be a direct signature of radial drift (e. g. ,  Trapman et al. 2019). This paper is organized as follows: Section 2 summarizes the target selection, the ALMA observations, and the calibration of the data. Section 3 presents the modeling of the data in the visibility plane for the continuum as well as in the image plane for the 12 CO and 13 CO emission. In Section 4, we discuss our results in the context of different origins for the seen substructures as well as the observed difference between the radial extent of the gas and dust.
Observations For sample completeness, we included the archival data of CIDA 1 in our list of targets, given that combining these previous archival observations results in a dataset with a similar sensitivity and angular resolution. For consistency with future works, the target properties used in this study (shown in Table  1 ) were taken from  Herczeg & Hillenbrand (2014) , with stellar masses derived following the method described in  Pascucci et al. (2016) , using distances inferred from Gaia DR2  (Gaia Collaboration et al. 2018). The distances in parsecs was calculated as the inverse of the parallax. The spatial distribution of our sample in the Taurus optical extinction map is shown in  The raw datasets were calibrated by applying the ALMA pipeline using the CASA version specified for each project  (McMullin et al.
In order to boost the signal-to-noise ratio (S/N) of each source, we performed self-calibration of the datasets in two steps: First we combined the compact configuration observations and performed self-calibration. Second, we combined those self-calibrated observations with the extended configuration observations and then self-calibrated again. Phase calibrations were applied until the improvement on the S/N was below ∼5%. Only 1 amplitude calibration was applied in each step. The overall S/N improvement was between 1. 5 ∼ 4. 0, depending on the source. The only source where self-calibration was not possible was J0415, because the initial S/N of 9 was too low for improvements. The final continuum images were generated using a Briggs robust parameter of 0. 0 for CIDA 1 and 0. 5 for the remaining sources.
Therefore, our observations only allowed us to directly detect deviations from a simple Gaussian profile in the disks where the extent of the emission is consistently larger than the synthesized beam size. CIDA 7 and J0420 are a good example of the limitations that our datasets have when detecting substructures. Even though we are unable to confirm the existence of dust substructures in these systems, the UV-plot in Fig. 2  of CIDA 7 shows some structure which is not described by a Gaussian profile, while the residual image of J0420 suggests that there might be more substructured dust emission that is not described by a single centrally peaked Gaussian in these disks. We lack the resolution and sensitivity to confidently characterize them. Given that these two disks are not totally dust depleted, the expected efficient radial drift must have been counteracted by a dust trapping mechanism.
(  2018 )), and the N 2 iceline which goes from ∼ 12 ∼ 15K. The iceline location was calculated for each star using the parameters shown in Table  1 , and the results are shown in Figure  5. In the right panel of Figure  5 , the positions of the detected substructures are displayed as a function of the root of stellar luminosity. Most of the substructures detected lie within the region where the CO iceline is identified. However, the role that the CO iceline plays in the morphology of our disk is not conclusive from our datasets. Even if we neglect the uncertainties introduced by the stellar parameters and the disk temperature, it is not clear if the structures that were generated by an iceline would result in a ring peaked at the iceline position or in a gap  (Pinilla et al. 2017b; van der Marel et al.
MHO 6 In MHO 6, the modeling indicates the existence of a central cavity that is slightly asymmetric. Several processes   5 ) and plotted with a black curve. The blue curve shows the best radial profile obtained from the continuum UV-modeling, which was normalized to the peak emission. Vertical red and light blue shaded regions show the possible locations of the CO (light red) and N2 (light blue) icelines. Right panel: Disk radius is shown versus the square root of stellar luminosity ( √ L ). The shaded regions show the iceline location for CO (light red) and N2 (light blue), obtained from equation (  6 ). The peak location of the modeled continuum emission rings are shown in squares, while the gap locations of J0433 are shown with dots. The lower line in each target marks half of the theoretical resolution given by the longest baseline for each dataset, as measured from the center, and the upper line marks the continuum R90.
The integrated velocity map contains the emission of both sides as if they were the same, and thus parameters such as M or ψ from Z(r, ψ) ∝ r ψ could not be recovered reliably. This issue is not an exclusive problem in VLMS disks, but it applies to all the gas measurements with a high angular resolution and poor S/N. Future approaches to accurately recover M should consider more robust methods, such as UV-modeling (similar to the DiskJockey code from  Czekala et al. 2015). MHO 6 is a good candidate to further study the kinematics, substructures, and the physics of planet formation in VLMS. Its brightness allows high S/N observations at high angular resolution with non-prohibitive integration times. Combining the datasets presented in this paper, plus an observation of ≥ 5 hr of time on source with ALMA using long baseline configurations should have enough resolution and sensitivity to precisely characterize the kinematics of the CO isotopologues, as previously done with disks around T-Tauri and Herbig stars (e.
Our UV-modeling of J0433 suggests that this disk could have two rings located at 21 and 32 au. However, we cannot confirm the separation between both at the 1 σ errorbar. We estimate that a planet of ∼ 0. 1 M Jup in mass could explain the first gap-ring. The substructures were detected within the region where the CO iceline could be located. Our current datasets lack the necessary S/N and resolution to properly characterize the vertical and radial temperature profile of the CO isotopologues, and so future deeper observations will be needed to determine if the iceline played any role in triggering or maintaining the substructures observed. -Smooth disks: The dust disks in CIDA 7, J0420, and J0415 are the less radially extended, less massive disks of our sample. With an angular resolution of 0.
Acknowledgements We thank  Timmy Delage  and  Reema Joshi  for their very helpful comments. We also thank  Sean M. Andrews  for the insightful discussions, which significantly improved this manuscript. N. K. and P. P. acknowledge support provided by the  Alexander von Humboldt Foundation  in the framework of the  Sofja Kovalevskaja Award  endowed by the  Federal Ministry of Education and Research. This Project has received funding from the  European Union 's  Horizon 2020 research and innovation programme  under the  Marie Sklodowska-Curie  grant agreement No  823823  (DUSTBUSTERS). This work was partly supported by the  Deutsche Forschungs-Gemeinschaft (DFG, German Research Foundation ) -Ref no. FOR 2634/1 TE 1024/1-1. This paper makes use of the following ALMA data: ADS/JAO. ALMA# 2012. 1.
Acknowledgements The authors gratefully acknowledge the support from  DGHE, Directorate General of Higher Education , the  Magnetically Separable Fe3O4/SiO2/TiO2 Photocatalyst 245 Makara J. Sci. December 2021  Vol. 25  No. 4  Republic of Indonesia  under program bilateral collaboration " Hibah Kolaborasi Luar Negeri  (HKLN);" and  Universitas Indonesia Research Cluster Program for Titania Photo Electrocatalysis (TiPEC) , and  Doctoral Research Support  Grant No:  1864/UN2. R12/ HKP. 05. 00/2015 ; and  NKB-319/UN2. RST/HKP. 05. 00/ 2021. The Scholarship support from The  State Ministry of Research and Technology (SMRT), Republic of Indonesia , for A. F. is also acknowledged.
Multipole-based databank approaches. Multipole parameters can be calculated theoretically from synthetic structure factors of model compounds and stored in tables according to the atom type defined in its chemical environment (Invarioms 26 or UBDB  27  ). Alternatively, such multipole databanks can be constructed from averaged experimental electron densities (ELMAM  28  ). Multipole parameters are then transferred from the databank to the compound under investigation, and non-spherical atomic form factors are calculated for use in the refinement on the fly from the transferred multipole populations. Although such refinements produce, e. g. , better structural parameters for hydrogen atoms,  29  they are currently restricted to organic and bio-organic compounds, for which the number of atom types is manageable.
NoSpherA2 NoSpherA2 brings wavefunction calculations, non-spherical atom partitioning, subsequent atomic form factor calculation, and finally least-squares refinement together under the umbrella of the freely available Olex2 software. 64 It is presented here utilizing the HAR non-spherical structure refinement method, but it is compatible with other flavors of (X-ray and electron) non-spherical structure refinement as well. Besides the NoSpherA2 method developments discussed below, the advantages gained within HAR by switching from the Tonto to the olex2. refine refinement engine are manifold and significant. It allows HAR to access the use of restraints and constraints, hydrogen atom riding models, correct crystallographic description of special positions, refinement of partial occupancies, twinning models, solvent disorder treatment via BYPASS, different choices of weighting schemes, and many more options.
Therefore, the corresponding atomic form factors are no longer real, but complex-valued functions of the Miller indices. The idea behind the flexible approach to non-spherical structure refinement that underlies NoSpherA2 is to provide these complex-valued form factors of each atom within the unit cell via a table given in a file provided from plugin software (. tscfile). 65 The underlying total electron density can be provided by quantum-mechanical calculations or other sources. For molecules that are related by symmetry within the unit cell, only the form factors of atoms within the asymmetric unit are required, since the geometric transformation from an atom in this asymmetric unit to an equivalent atom in the unit cell corresponds to a transformation of the Miller indices of the corresponding non-spherical atomic form factor.
NoSpherA2 GUI and interface Figure  2  summarizes the interplay of different steps of the nonspherical structure refinement and related software programs interfaced by NoSpherA2. At first, the input for the refinement is selected in the Olex2 graphical user interface (GUI) (Figure  2 ) from a grown structure if necessary. The atomic coordinates of this structure are then transferred to the chosen quantummechanical software in form of a. cif or. xyz file. At present, ORCA,  67  Gaussian,  68   The entire cycle visualized in Figure  2  can be iterated manually or automatically until convergence in all refined parameters within less than 1% of their standard uncertainties is reached. This automatically iterated refinement is consistent with the standard definition of Hirshfeld Atom Refinement (HAR).
Visualization of derived properties and functions Olex2 natively includes engines for the generation of two-and three-dimensional maps and plots of functions for the representation of residual electron densities. In the course of the implementation of the NoSpherA2 software, we have significantly extended the plotting options from dynamic and static deformation electron density and Laplacian of electron density maps to properties that can only be obtained with wavefunction information. This includes the electron localizability indicator ELI,  77  electrostatic potentials, molecular orbitals, and the non-covalent interaction NCI index. 78 herefore, all pictures in this paper except for Figures  1  and 4  (b) are generated with the Olex2 software.
Validation of HAR in NoSpherA2 The multi-temperature X-ray and neutron-diffraction data sets of L-Ala and Gly-L-Ala represent a well-established benchmark set of structures already used in previous tests and validations of HAR. 32, 39, 79 Here, five X-ray datasets of Gly-L-Ala and three X-ray datasets of L-Ala were refined at HF/6-311G(d,p) using six different refinement techniques each (Table  2 ). iv HAR NoSpherA2 ORCA Tonto 1/σ 2 (F 2 ) v HAR NoSpherA2 ORCA Tonto Shelxl-type vi HAR NoSpherA2 ORCA NoSpherA2 1/σ 2 (F 2 ) In all models and datasets, the hydrogen atom positions and displacement parameters were freely refined. In all HAR models, hydrogen atoms were refined anisotropically. Figure  3  shows an indicative comparison between the residual density distributions after a standard (IAM) refinement and a HAR with model vi.
Software Details To make the refinements convenient, a NoSpherA2 Graphical User Interface (GUI, Figure  2 ) was added to the "Refine" tab inside the Olex2 GUI which appears once the NoSpherA2 tickbox is activated. "Update Table" asks for the source of the. tsc file. For HAR, this means that either the QM software for the. tsc generation or an existing. tsc file must be chosen to be used in the least-squares refinement. The remaining user-specified options concern settings for all of the three major job steps. Basis sets and methods are pre-selected according to the QM software choice. PBE/def2-SVP is the minimal level for quick and yet reliable results. Most results in this paper are based on PBE/def2-TZVPP, because the PBE-GGA density seems to be well suited for the HARs, 101 whereas higher basis sets seem to be necessary for accurate atomic displacement parameters.
0001 e. According to the choice of integration accuracy used here for the atomic form factor calculation, a corresponding accuracy will also be selected for the wavefunction calculation in the QM software. All HARs presented in the Results and Discussion part (section 4) were carried out with the following settings: source of. tsc: ORCA; basis set: def2-TZVPP (except Os where x2c-TZVPP was used); method: PBE; relativistics: not used (except for Os); SCF Conv. Thresh. : NormalSCF; SCF Conv. Strategy: NormalConv; H Aniso: activated (if not mentioned otherwise); No Afix: activated; updated Shelxl-type weighting scheme: activated; automatic HAR; Integr. Accuracy: high; EXTI: not activated; DISP: activated. Cluster charges were not used for the simulation of the crystal field. Only for validation purposes and for the Oscontaining compound, settings were varied.
Other refinement details are shown in Table  3  as well as in the Crystallographic information files deposited with the Cambridge Structural and Inorganic Crystal Structure Database (CCDC-2034385 to 2034389, 2035147 to 2035148). The setup for benchmarking the heavy element refinements was a 4-core 2. 81 GHz hyperthreaded laptop with 16 GB RAM and no solid-state drives using 7 threads for ORCA. A significant part of the calculation was the evaluation and saving of relativistic integrals, which is similar for all functionals (approx. 125 s in these calculations). Apart from that, the PBE calculation was significantly faster than the MO6-2X calculation (161 % Please do not adjust margins Please do not adjust margins longer), and still faster than the B3LYP calculation (13% longer). Furthermore, the results of the refinement using PBE are very similar to those of the more sophisticated functionals, so the use of PBE for all-purpose refinements is suggested, even when heavy elements are involved.
Origin of datasets and synthesis of compounds For the validation part (section 3), previously published X-ray structure factors of L-alanine (L-Ala)  104  and glycyl-L-alanine (Gly-L-Ala)  32  were used. For comparison, the results of neutrondiffraction studies at the respective same temperatures were used, from ref. 39  for L-Ala, and from ref. 105  for Gly-L-Ala. X-ray structure factors of the CO2-hydroquinone clathrate (HQ-CO2) were taken as deposited in the Cambridge Structural Database belonging to ref. 46  , whereas those of the tetrahydropyrido [2,3b]pyrazine derivative (THPP) stem from ref. The molecule in HQ-CO2 is located in a special crystallographic position. For the wavefunction calculations, we constructed a cluster of 12 hydroquinone molecules around the trapped CO2 molecule enclosing the void (Figure  4 ), but only a fraction of that cluster was refined as the crystallographic asymmetric unit, which consists of half a molecule of hydroquinone and half a CO2 molecule (Z = 9, Z' = 0.
Conclusions and Outlook In this work, we have generalized ´non-spherical structure refinement´ so that any flavor of quantum-crystallographic crystal-structure treatment can be linked with the established and modern free software Olex2, and specifically with its comprehensive refinement engine olex2. refine. The capabilities of NoSpherA2 are demonstrated here for the example of Hirshfeld Atom Refinement, which can now be applied to disordered structures, inorganic periodic network compounds including salts, and compounds containing heavy elements. developments also open HAR to the fields of protein crystallography, as well as inorganic and metal-organic materials. In this respect, as a core chemical result, we demonstrate that there is a strong directional dependence of bonding and non-sphericity of electron density in fluorite CaF2, although it is generally assumed that it consists of spherical ions.
We will investigate this point further by applying nonspherical refinements to other ionic species. HARs in NoSpherA2 significantly faster than previous implementations of HAR and often more accurate. In principle, any modern quantum-mechanical software can now be used for the theoretical steps, demonstrated here by the use of ORCA, which is a QM software freely available for academic use. The PBE DFT method with triple-zeta basis sets is recommended for a good balance between accuracy and speed. This is even true for heavy transition metals, where relativistic extensions are necessary. NoSpherA2 also enabled us to pin down the problems in the crystallographic refinement of heavy elements and show pathways for further developments in the field. Since the format file underlying NoSpherA2 is entirely general, interfacing Olex2 with other flavors of X-ray non-spherical structure refinement is simple and straightforward.
Acknowledgements The authors acknowledge much feedback of testers and users of NoSpherA2 alpha versions leading to optimization of the GUI and code and many bug-fixes. We thank  Professor Hans-Beat Bürgi  for continuous constructive criticism during the development of NoSpherA2, and  Dr. Georgia Cametti  for the crystal of CaF2. We gratefully acknowledge the support for LM through the  Intensive Industrial Innovation Programme run by Durham University  and funded by the  European Regional Development Fund (ERDF).