Chem 125 Lecture 5 9/12/08 Projected material This material is for the exclusive use of Chem 125 students at Yale and may not be copied or distributed further. It is not readily understood without reference to notes from the lecture. Despite Earnshaw, might there still be shared-pair bonds and lone pairs? Scanning Probe Microscopies (AFM, STM, SNOM) are really powerful. Sharp points can resolve individual molecules and even atoms but not bonds Lux A lonely architectural curiosity on Sterling Chemistry Laboratory at Yale University (1923) Micrographia Robert Hooke (1665) “But Nature is not to be limited by our narrow comprehension; future improvements of glasses may yet further enlighten our understanding, and ocular inspection may demonstrate that which as yet we may think too extravagant either to feign or suppose.” Strong 400 nm Scattering No 800 nm Scattering “Thickness” ~ 200 nm Oil Path Difference = 400 nm =1l = 0.5 l Interference upon Scattering Water Chris Incarvito’s New Toys User Operated - CCD Detector ~$200K X-Ray Tube ~$350K Image Plate "Seeing" Individual Molecules, Atoms, and Bonds? Problem: l What IS light? In What Way is Light a Wave? Force on Charge at One Position Up Charged Particle 0 Down Time Force at Different Positions - OneTime In What Way is Light a Wave? Up Charged Particle 0 Down Position Accelerated Electrons “Scatter” Light direct beam Why don’t protons or other nuclei scatter light? Too heavy! Interference of Ripples Angular Intensity Distribution at great distance depends on Scatterer Distribution at the origin By refocussing, a lens can reassemble the information from the scattered wave into an image of the scatterers. But a lens for x-rays is hard to come by. Be sure to read the webpage on x-ray diffraction. "Seeing" Molecules, Atoms, Bonds Collectively by X-Ray Crystallography Blurring Problem from Motion and Defects Blurring Problem Time Averaging Space Averaging in Diffraction (Cooperative Scattering) Advantage for SPM (Operates in Real Space) Shadow of Frau Röentgen’s hand (1896) In 1895 Röntgen Discovers X-Rays In 1912 Laue Invents X-Ray Diffraction CuSO4 Diffraction (1912) Wm. Lawrence Bragg (1890-1971) Determined structure of ZnS from Laue's X-ray diffraction pattern (1912) (1915) Courtesy Dr. Stephen Bragg Youngest Nobel Laureate B-DNA R. Franklin (1952) Science, 11 August 2000 >100,000 atoms + hydrogens! 25 nm (250 Å) What can X-ray diffraction show? Molecules? Atoms? Bonds? How does diffraction work? Like all light, X-rays are waves. Wave Machines Bragg Machine http://www.eserc.stonybrook.edu/ProjectJava/Bragg/ in & out same phase Breaks? by permission, Konstantin Lukin Two Scattering Directions are Always Exactly in Phase Specular perpendicular to scattering vector Specular All electrons on a plane perpendicular to Direct the scattering vector scatter in-phase at the specular angle ! Electrons-on-Evenly-Spaced-Planes Trick 3 4 2 1 Electrons-on-Evenly-Spaced-Planes Trick Total Electrons Suppose l & angle such that: 3 +4 1l +2 2l 3l 3 4 2 1 +1 10 Net in-phase scattering Electrons-on-Evenly-Spaced-Planes Trick Total Electrons 3 3 +4 -4 0.5l +2 +2 1l 1.5l 3 4 2 1 Suppose first path difference is half a wavelength, because of change in l (or angle) +1 -1 10 0 Net in-phase scattering spacing = 10.8 cm ………………….. Q. What is the line spacing? DIFFRACTION MASK (courtesy T. R. Welberry, Canberra) 10.6 m View from Ceiling 633 nm End of Lecture 5 Sept 12, 2008