1. Chem 125 Lecture 5 9/15/06 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.

2. Some Resonance Structures for H, C, N, O Isomers For quantum-calculated local-minimum-energy atomic arrangements

3. H, C, N, O isomers C in middle H C N O : : : H C N O : : : H C N O : : : + _ H C N O : : : + _ charge separation

4. H C N O : : : : H C N O : : : + _ : H C N O : : + _ + _ H C N O : : : : + _ H C N O : : : bad charge sestet bad charge H, C, N, O isomers N in middle

5. H C N O : : : : + _ H C N O : : : : _ + H C N O : : : : _ + H C N O : : : : + _ sestet bad charge sestet H, C, N, O isomers O in middle

6. H C N O : : : H C N O : : + : _ H C N O : : : : sestet bad charge H, C, N, O isomers cyclic H C N O : : : + _ sestet H C N O : : : + _ : bad charge Can’t even be calculated (opens up)

7. HNCO isomers H C N O : : : H C N O : : : H C N O : : : H C N O : : : : H C N O : : : + _ H C N O : : : : + _ H C N O : : : : _ + H C N O : : + : _

8. 150 100 50 0 200 kcal/mole H C N O H C N O H C N O H C N O H C N O H C N O H C N O H C N O E calc

9. References: Most of these structures and energies were calculated at a very high level of theory as reported in Journal of Chemical Physics, 120, 11586-11599 (2004). The much less stable structures with O in the middle were calculated using the highest level of theory available in the Spartan 04 package of quantum programs. This program could not find an energy minimum for the cyclic structure with H on oxygen.

10. Levitator by Martin Simon (UCLA) Eppur sta fermo

11. J.J. Thomson (1856-1940) Electron (1897) Plum-Pudding Atom

12. "[We can] solve the special case where the corpuscles are confined to a plane." Thomson's Model of Electron Configuration "consider the problem as to how 1…2…3…n corpuscles would arrange themselves if placed in a sphere filled with positive electricity of uniform density…" “distributed in the way most amenable to mathematical calculation” in

13.     Vortex Lattice Models (Greg Blonder www.genuineideas.com)  

14. "[We can] solve the special case where the corpuscles are confined to a plane." Thomson's Model of Electron Configuration "consider the problem as to how 1…2…3…n corpuscles would arrange themselves if placed in a sphere filled with positive electricity of uniform density…" "the equilibrium of eight corpuscles at the corners of a cube is unstable." in

15. "I have ever since regarded [the cubic octet] as representing essentially the arrangement of electrons in the atom" G. N. Lewis (1923) Was Lewis ignorant of Earnshaw's Theorem?

16. Conclusion of Valence and the Structure of Atoms and Molecules G. N. Lewis (1923) "if we use the electron as a test charge to determine the properties of the simplest possible electric field, namely, the field about a hydrogen nucleus, we appear to find that this field is not a continuum but is strikingly discontinuous." The Future of the Quantum Theory The Discontinuity of Physico-Chemical Processes

17. The Electron in Chemistry J. J. Thomson (1923) … if [electron-nuclear attraction] were to vary strictly as the inverse square of the distance we know by Earnshaw's theorem than no stable configuration in which the electrons are at rest or oscillating about positions of equilibrium is possible... … then a number of electrons can be in equilibrium about a positive charge without necessarily describing orbits around it. I shall assume that the law of force between a positive charge and an electron is expressed by the equation c r atomic length scale Couloumb

18. Quantum Mechanics (1926) kinetic energy reformulated to explain electron clouds and produce an "inverted" plum-pudding atom. Cubic octets and ad hoc force laws soon disappeared from conventional Chemistry and Physics But shared-pairs and lone-pairs remained useful tools for discussing structure and bonding.

19. Earnshaw: No energy minimum for point charges Classical

20. Despite Earnshaw, might there still be shared-pair bonds and lone pairs?

21. How do you know? By Seeing? Feeling?

22. Problem: Inconceivably Small ?

23. OCCULT CHEMISTRY A SERIES OF Clairvoyant Observations on the Chemical Elements BY ANNIE BESANT, P.T.S. AND CHARLES W. LEADBEATER Reprinted from the Theosophist. T HEOSOPHIST O FFICE, A DYAR, M ADRAS, S. T HEOSOPHICAL P UBLISHING S OCIETY, L ONDON AND B ENARES C ITY. 1909 (105 pp.) 1919 (123 pp.) 1951 (400 pp.)

24. Mrs. Annie BESANT P.T.S. (1847-1933) Curuppumullage JINARAJADASA P.T.S. (~1877-1953) "Bishop" Charles Webster LEADBEATER (1847 - 1932) The Occult Chemists (1895-1932)

25. H O N (1895) 18 290 261

26. Helium 72 Lithium 127 Iron 1008 Neon 360 Occult Atoms

27. 4f orbital e-density Occult Atoms Bases for Belief: 1) Evidence "cross-examine an assertion" 2) Taste matures with experience

28. 4f orbital e-density Sodium 418 Occult Atoms

29. Na 2 CO 3 (1924) "note that this trian- gular arrangement of O 3 has just been deduced by Bragg from his X-ray analysis of Calcite"

30. Benzene (1924) "each of the three valencies of each Carbon are satisfied by Hydrogen, and the fourth valency, which some have postulated as going to the interior of the molecule, does actually do so." Cf. Wiki: Question 6 “Credit” for use?

31. Benzene “Resonance” H H H H H H C C C C C C H H H H H H C C C C C C H H H H H H C C C C C C (1889)

32. 1 cm 3 of water ≈ 10 24 molecules molecules / cm Are Molecules Unobservably Small for "Vulgar" Eyes?

33. 10 5 Lecture Room ~10 m Hair ~100  m Nucleus ~10 fm Molecule ~1 nm (small atom ~ 0.1 nm = 1 Å) 10 1 10 -4 10 5 10 -9 10 5 10 -14 10 5

34. Query 31 …the Attraction [between glass plates separated by a thin film of Oil of Oranges] may be proportionally greater, and continue to increase until the thickness do not exceed that of a single Particle of the Oil.

35. 3/8  10 -6  2.54 cm/inch ≈ 10 -6 cm = 100 "waters" ! Newton Opticks (1717) p. 369

36. flat to flat 62 mm convex to flat Newton’s Rings ~1 mm gap at rim 1 mm

37. p. 175 Newton Opticks (1717)  = cos -1 (0.29"/(12"  51')) = 89.973° air gap 0.29" = (12  51)(1-sin  ) = 7  10 -5 inch = 1.8  m  51'

38. Simpler Measurement of Smaller Distance 1774

39. End