Computational Chemistry

(Steven Felgate) #1

  1. MM history: (a) References 1. (b) Engler EM, Andose JD, Schleyer PvR (1973) J Am Chem
    Soc 95:8005 and references therein. (c) Molecular mechanics up to the end of 1967 is
    reviewed in detail in: Williams JE, Stang PJ, Schleyer PvR (1968) Ann Rev Phys Chem
    19:531

  2. (a) Westheimer FH, Mayer JE (1946) J Chem Phys 14:733. (b) Hill TL (1946) J Chem Phys
    14:465. (c) Dostrovsky I, Hughes ED, Ingold CK (1946) J Chem Soc 173. (d) Westheimer FH
    (1947) J Chem Phys 15:252

  3. (a) Ma B, Lii J-H, Chen K, Allinger NL (1997) J Am Chem Soc 119:2570 and references
    therein. (b) In an MM4 study of amines, agreement with experiment was generally good:
    Chen K-H, Lii J-H, Allinger NL (2007) J Comp Chem 28:2391. (c) Five papers, using
    MM4, on Alcohols, ethers, carbohydrates, and related compounds. J Comp Chem 24
    (2003): Allinger NL, Chen K-H, Lii J-H, Durkin KA, 1447; Lii J-H, Chen K-H, Durkin A,
    Allinger NL, 1473; Lii J-H, Chen K-H, Grindley TB, Allinger NL, 1490; Lii J-H, Chen K-H,
    Allinger NL, 1504; (2004) J Phys Chem A 108; Lii J-H, Chen K-H, Allinger NL, 3006

  4. (a) Information on and references to molecular mechanics programs may be found in
    references 1 and the website of reference 1a. (b) For papers on the popular Merck Molecular
    Force Field and the MM4 forcefield (and information on some others) see the issue of J Comp
    Chem 17 (1996)

  5. The force constant is defined as the proportionality constant in the equation force¼kx
    extension(of length or angle), so integrating force with respect to extension to get the energy
    (¼force x extension) needed to stretch the bond givesE¼(k/2)(extension)^2 , i.e.k¼force
    constant¼ 2 kstretch(or 2kbend)

  6. (a) A brief discussion and some parameters: Atkins PW (1994) Physical chemistry, 5th edn.
    Freeman, New York, pp 772, 773; it is pointed out here that e$r/sis actually a much better
    representation of the compressive potential than is r$^12. (b) Moore WJ (1972) Physical
    chemistry, 4th edn. Prentice-Hall, New Jersey, p 158 (From Hirschfelder JO, Curtis CF,
    Bird RB (1954) Molecular theory of gases and liquids. Wiley, New York). Note that ourknb
    is called 4ehere and must be multiplied by 8.31/1000 to convert it to our units of kJ mol$^1

  7. Infrared spectroscopy: Silverstein RM, Bassler GC, Morrill TC (1981) Spectrometric identifi-
    cation of organic compounds, 4th edn. Wiley, New York, Chapter 3

  8. Different methods of structure determination give somewhat different results; this is discussed
    in reference 4(a) and in: (a) Ma B, Lii J-H, Schaefer HF, Allinger NL (1996) J Phys Chem
    100:8763 and (b) Domenicano A, Hargittai I (eds) (1992) Accurate molecular structures.
    Oxford Science, New York

  9. To properly parameterize a molecular mechanics forcefield by calculations only high-level
    ab initio (or density functional) calculations would actually be used, but this does not affect
    the principle being demonstrated

  10. Reference 1b, section 4.8

  11. MM3: Allinger NL, Yuh YH, Lii J-H (1989) J Am Chem Soc 111:8551. The calculation was
    performed with MM3 as implemented in Spartan (reference 15)

  12. Eksterowicz JE, Houk KN (1993) Chem Rev 93:2439

  13. Smith MB, March J (2000) March’s advanced organic chemistry. Wiley, New York, pp
    284–285

  14. Spartan is an integrated molecular mechanics, ab initio and semiempirical program with an
    input/output graphical interface. It is available in UNIX workstation and PC versions:
    Wavefunction Inc., http://www.wavefun.com, 18401 Von Karman, Suite 370, Irvine CA
    92715, USA. As of mid-2009, the latest version of Spartan was Spartan 09. The name arises
    from the simple or “Spartan” user interface.

  15. Ref. [1c], pp 182–184

  16. Gundertofte K, Liljefors T, Norby P-O, Pettersson I (1996) J Comp Chem 17:429

  17. Comparison of various forcefields for geometry (and vibrational frequencies): Halgren TA
    (1996) J Comp Chem 17:553


80 3 Molecular Mechanics

Free download pdf