PDF-4+

1. PDF-4+ The Powder Diffraction File Release 2006

2. Index – Use direct links to skip to the section • Fundamentals • Design and Purpose • Data sources and collaborations • Quantitative Analysis with PDF-4+ • Material Data Sets (Entries) • Pattern Simulations • Molecular Display • Searches and Data Mining • Pattern Fitting • Combining Tools – Analyzing polymorphs

3. Notice This presentation gives an overview of features and capabilities found in the Powder Diffraction File (PDF), specifically PDF-4+ Release 2006. This presentation represents a small portion of the capabilities in the database. The presentation focuses on the database and not on the capabilities of the database when combined with the world’s leading data analysis programs. The database itself contains over 500 pages of help file documentation. This includes definitions and terms of the classifications and calculations used in the database.

4. Fundamentals

5. PDF-4+ Basic Capabilities • PDF-4+ contains 254,873 entries. • Entries contain > 85 data fields, some fields such as d, I, h,k,l and atomic parameters may contain dozens to hundreds of data points. • There are 65 different data display options. • There are 44 search options. Display and search options can be combined and permuted using a JAVA interface. This results in nearly endless combinations for data display and analysis, only a few of which are described here.

6. Powder Diffraction File (PDF) PDF Databases are designed to work with most commercial diffraction analysis software packages. The ICDD works with software distributors so that the PDF seamlessly interfaces to their software. Many features in the database are specifically designed for distributor use. A list of compatible software and distributors can be found here.

7. CompanySoftware Bede Bede Search/Match Bruker AXS EVA, DiffractPlus, PolySNAP, Topas Bruker AXS SAS DiffractPlus, EVA (formerly Socabim) Crystal Impact Match, Endeavor Digital Data Corp MacPDF EDAX ACT, OIM GE Inspection Rayflex Search/Match GBC Traces HKL Technology Flamenco Inel WinFit ITAL Structures WinDust32, WinSearch32 Kratos (Shimadzu) PDF-2 Search Software CompanySoftware MDI JADE, jPOWD RIQAS, RUBY Overseas X-ray PDF Plus Oxford Instruments Flamenco Oxford Cryosystems Crystallographica PANalytical X’Pert Highscore Plus Rigaku JADE, jPOWD, RIQAS, RUBY RMS Kempten ADM/PADS Sine Theta 2TdST STOE & Cie GmbH WinX Pow Tasker Applications TXRDWIN Thermo Electron WinXRD ZDS SEARCH/MATCH, QUANT Diffraction Analysis Softwareinterfaced to PDF Databases Please check with the vendor to match their software with the specific release of the PDF database (year and type, i.e. PDF-4+ Release 2006).

8. Design & Purpose

9. All PDF Databases are designed for rapid material identification.This differentiates a PDF database from all other databases of crystallographic or physical property data.If you are working on a knownmaterial another database maybe more appropriate for your work.

10. Powder Diffraction File • Rapid Material Identification with the PDF • The database is designed to use input data and match it to • candidate reference materials. • Most matching is done by comparing sets of d-spacing and Intensities, • however it can also be done by chemistry, properties, structural • and crystallographic classifications – using dozens of different • searches. • All data are converted to a standardized format for rapid search. • There are many embedded indexes facilitating searches. • Data entries are extensively cross referenced to other entries and to • physical and chemical measurements. • Data are extensively classified by chemical and structural types; • each classification can be searched.

11. Sources of Data

12. The Powder Diffraction FilePDF-4+ Database Data Sources for the Database 1) Publications, journals, scientific periodicals and theses 2) ICDD Grants for new materials (~60 annual grants) 3) Data collections donated by companies or individuals 4) Data from other Database organizations that they collect from scientific publications The Powder Diffraction File contains a compilation of data from 5 global databases. PDF-4+ uses 4 database sources.

13. PDF Databases – Continuous growth and change • Data on new materials are being constantly collected and published by laboratories around the world so the PDF database continually grows. • With time, data quality has steadily improved in both accuracy and precision. (Better hardware, optics, software and computational power as a function of time). This leads to improved accuracy in the database and the diffraction method of analysis. A major function of the ICDD editorial system is to evaluate quality and standardize data that has been collected by global sources over decades of time. The quality evaluations and standardization processes are also updated continually and the entire database gets reviewed each time.

14. Powder Diffraction File – Database Collaborators Cambridge Structural Database (CSD) ICSD NIST Linus Pauling File (LPF)

15. Each PDF database contains data from several database sources PDF-4+ 254,873 Entries PDF-4/ Organics 312,355 Entries Release 2007 PDF-2 186,107 Entries ICDD, NIST, ICSD + LPF ICDD-organics + CSD ICDD, NIST, ICSD

16. PDF-4+ The PDF-4+ and its subset, PDF-4/Minerals, are the only PDF databases that contains data from the Linus Pauling File (LPF). The LPF is currently the largest single global source of inorganic atomic coordinates and crystallographic parameters. It is also a large source of data on inorganic materials, many with unique compositions. This data is added to inorganic materials data from ICDD, NIST and ICSD to form the comprehensive data collection in PDF-4+.

17. 500,000 Material Data Sets and Growing!Data from global sources – collected, translated, edited and standardized PDF-4/ Organics 60 Years PDF-4+

18. PDF-4+ More Data and New Data Distribution of data by number of elements, PDF-2 and PDF-4+ Unique Formula

19. Database Codes The first two digits in any PDF number contains the database Code. For example PDF 04-005-4319 is the PDF number for an Fe3O4 entry that is sourced from the Linus Pauling File (04-LPF).

20. Material Data Sets (Entries) Each entry contains Chemical information and nomenclature Experimental conditions Diffraction data including d,I and h,k,l listings Journal reference and bibliographic citations Crystallographic data Individual entries, such as the one for Acetaminophen, PDF 00-039-1503, displayed on the left may contain thousands of alphanumeric data fields. Print display of a PDF entry

21. Acetaminophen PDF 00-039-1503 A multi-page nested display, shown below, is used to display the data in PDF-4+. Printed Form for Data

22. Quantitative Analysis with PDF-4+

23. PDF-4+ The PDF-4+ database is designed for rapid identification and quantitative analysis. Quantitative analysis can be performed by any of three different methods and the database provides the properties required these analysis techniques.

24. Quantitative Analysis and PDF-4+ MethodDatabase Quantity Required by of Quantitationthe Method Reference Intensity Ratio 165,923 Entries with I/Ic Rietveld Analysis 98,291 Structures with atomic parameters and unit cells Full Pattern Analysis 254,873 entries all with full digital patterns that can be modified for wavelength, radiation (x-rays, neutrons, electrons) instrumental and specimen effects

25. Full Pattern Analysis Digital patterns of ~150 A Cellulose II and Ib, with crystalline stearic acid. Experimental data on a natural product tablet in blue.

26. Automated Quantitative Analysis by XRD PDF-4+ databases provide reference data, viewing software, critical physical properties and crystallographic properties required for quantitative analysis. The database is designed to work with many software packages, including those of all major global instrument manufacturers. These software packages provide the required calculations and refinements for automated quantitation utilizing the data in PDF-4+. With modern software and databases this operation is seamless and can be often be done in minutes.

27. Features – The PDF Entry

28. 1 The main entry page includes several display options 1 and data in nested display Pages. 2 2 These are activated by the “point” and “click” of a mouse.

29. 1 Display Options Pattern Simulations Electron Diffraction Simulation Electron Backscatter Pattern Digital Diffraction Pattern

30. 1 Display Options Molecular Dimensions & Graphics Molecular Graphics Bond Angles & Distances

31. 1 Pattern Simulations Options for the addition of multiple phases, instrument and specimen factors, wavelengths. Options for import/export and graphic display Calculations. Crystallite size simulation

32. Display Options – d,I Listings Rightclick the mouse to Undock pattern listing and compare data with different instrument configurations. Fixed Slit Variable Slit Integrated I Note how the intensities changes as a function of optical configuration, resolution.

33. 2 Data in Nested Display Print Forms

34. Data in Nested Display – Computer Display 2 Subfile designations, pattern cross references (active link), Pearson symbol and prototype assignment Opening page – status, formula, quality mark Experimental and Bibliographic reference Editors evaluation and database cross references Structure, symmetry, atomic positions, active link to atomic environment display

35. Display Fields in PDF-4+ ColorCoding Key • Fields filled in >80% of the 254,873 entries • Fields filled when the data is provided by the original source • Fields filled by an field expert editor, consultant or volunteer editorial task team • Quality indicator measurements

36. Display Fields Accessible from the Main Entry page through nested page displays Physical System Space Group Aspect Author Cell Volume Reference D calc D meas D structure SS/FOM Melting Pt Z R-Factor Error PDF PDF# Status Quality Mark Pressure/Temperature Chemical Formula Weight % Atomic % ANX Compound Name Mineral Name Common Name Experimental Radiation Wavelength Filter d-spacing type Cutoff Intensity type I/Ic Camera Diameter Reference Title Author Citation Crystal Space Group Z MW Crystal Cell Crystal Volume Crystal axial ratio Reduced Cell Reduced Volume

37. Display Fields Accessible from the Main Entry page through nested page display Only in PDF-4+ Optical alpha beta gamma Sign 2V Reference Structure TF type Coordinate Table Atom Number Wyckoff Position Symmetry x,y,z SOF (Site Occupancy) ITF (Isothermal TF) AET (Atom Environment) Symmetry Operator Anisotropic Temp Factors Miscellaneous CAS # PDF Cross References and status Pearson Symbol Prototype Structure LPF Prototype Mineral Classification Zeolite Classification Subfiles Entry Date Last Modification Date • Editorial • Editors Comments • includes comments • generated by statistical • analysis of the data • User Comments • Shared Comments 98,291 Structures in PDF-4+

38. Display Fields in PDF-4+ Expanded views of the d, I, h,k,l listing and stick figure. Both are interactive displays where the user can expand, sort and scale the data.

39. Searches and Data Mining

40. Searches and Data Mining • ICDD problem solving software • Completely re-written in Java • Powerful search and retrieval • Numerous display options • Flexible user-interface • Features based on our extensive RDB knowledge and user feedback

41. Searching Search Icon “Point and Click” Opening screen menu Main Search Page Searches are performed by using the search option on the program DDView+. This program is embedded in the database. If you use vendor display software you may have to start the program “ICDD PDF-4+ 2006” from your program menu to see the options described here. Every PDF-4+ database has this program. (It is an option for PDF-2).

42. Search • Central input form (Main Search Page) • 45 unique criteria in 7 categories • Multiple input methods: • Lists • Text • Numeric • Estimated Standard Deviation (ESD) • Ranges • Periodic Table • Composition Table • Logical Boolean operators • Powerful cumulative searches • Criteria selection awareness

43. Searches are activated by point and click operations or alphanumeric entry. Activated fields become highlighted in red. Multiple fields can be active. In this example search fields for LPF, star quality, primary, ambient data for Si and O were activated.

44. This search activated an empirical formula combined an elemental composition analysis with a specific space group and compound name. Input element composition analysis with error limits

45. Search Display - Results 2 The criteria matched 1,817 entries in PDF-4+ All 1,817 entries search results can be accessed through the scroll bar. 3 1 The search criteria are given in the search description.

46. Search Results- User Preferences Click on the “Preferences” Icon or Use the Fields drop down menu User selection of the display fields can be done by point and click interfaces or a drop down menu. The menu above allows the user to add, drop and change the display order.

47. Search Results Same search criteria as before but now the user defined order preferences are displayed: Mineral name, Quality mark, Reduced cell parameters, Pearson symbol and chemical formula. Minerals sorted Alphabetically. Reverse order by clicking on the Header.

48. Search Results – Display Algorithms & Calculations • Sorting algorithms: • Alphabetical • Alphabetical Formula Index • Numerical • Proprietary • Calculations: • Mean • Median • ESD Calculations Displayed Same search, the user can highlight any numerical field and obtain a mean, median and ESD for the entries.

49. Application Example 1:Phase Identification • From research we obtain the following data: • Pattern is cubic • Lattice parameter a=12.348(.010) Å • Pattern density is ρ=4.9(.1) g/cm³ • Pattern color is red • Pattern melting point is 677(5) °C • We then input these user data into DDView+ and look for possible solution(s).