Dihedral Parameterization

From: Venky (venky.agas_at_gmail.com)
Date: Mon Aug 20 2007 - 19:17:28 CDT

Hi,

I am trying to parameterize a small molecule using ab-initio calculations
and I am new to parameterization. I have a few questions regarding Dihedral
angle parameter determination.
I optimized the geometry of my molecule and used the lowest energy
configuration to generate Potential energy surface scan of a particular
dihedral angle rotation (rigid PES scan without optimization at each
rotation) and below are the energies obtained from the calculation.

*******************************************
Summary of the potential surface scan:

   N t16(deg) SCF
 ---- --------- -----------
    1 -179.9018 -1782.33483
    2 -167.9018 -1782.33287
    3 -155.9018 -1782.32715
    4 -143.9018 -1782.31720
    5 -131.9018 -1782.30308
    6 -119.9018 -1782.28451
    7 -107.9018 -1782.26171
    8 -95.9018 -1782.23616
    9 -83.9018 -1782.21000
   10 -71.9018 -1782.18683
   11 -59.9018 -1782.16332
   12 -47.9018 -1782.11096
   13 -35.9018 -1781.95668
   14 -23.9018 -1781.55212
   15 -11.9018 -1780.77154
   16 0.0982 -1780.21021
   17 12.0982 -1780.77625
   18 24.0982 -1781.55508
   19 36.0982 -1781.95792
   20 48.0982 -1782.11159
   21 60.0982 -1782.16350
   22 72.0982 -1782.18703
   23 84.0982 -1782.21022
   24 96.0982 -1782.23629
   25 108.0982 -1782.26192
   26 120.0982 -1782.28451
   27 132.0982 -1782.30301
   28 144.0982 -1782.31721
   29 156.0982 -1782.32717
   30 168.0982 -1782.33291
   31 180.0982 -1782.33483
 ---- --------- -----------

The graph is a single spike at 0 degrees with two minima at 180 and -180. I
tried to fit the data using the dihedral parameter equation...
V=Kchi(1+cos((n*chi)-d)) but the plot doesn't look like a cosine curve.
rather the energy rise is steep at its maximum (near 0 degrees) and the data
doesn't fit the equation.
I used n=1, d=0 and varied Kchi over chi= -180 to 180.

Is the procedure followed by me the right way to go about dihedral
parameterization? If then how do I go about fitting the PES energies to the
Dihedral equation.

Thanks a lot in advance...

Venky

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