CCL: Dihedral angle: DFT vs Crystal structure



I would look at the unit cell for the crystal and see how the dihedrals are situated.  Often it is obvious why those particular structural features differ significantly from phase to phase (and sometimes it is not so obvious).



Cheers,

Flick

_______________

William F. Coleman
Professor of Chemistry
Wellesley College
Wellesley MA 02481






On Wed, Aug 29, 2012 at 2:42 AM, Adedapo Adeyinka u11335132:-:tuks.co.za <owner-chemistry*ccl.net> wrote:
Dear Gopakumar,
                         Like Cina said it would be impossible to reproduce the geometry of a molecule in the solid phase with gas phase computations. However from my experience calculations on molecules in solvent might be able to predict the geometry in solid phase. So you can try to do computations on your molecule using DFT with the PCM solvation model and the UFF force field.
 
Adeyinka Adedapo
Department of Chemistry,
University of Pretoria, South Africa

On 28 August 2012 16:06, G. Gopakumar gopakumar.gopinadhan]^[gmail.com <owner-chemistry-.-ccl.net> wrote:
Dear CCL members,

     I was calculating a molecule (71 atoms) for which the crystal structure is
known. However, according to my calculation, one of the dihedral angles shows
large mismatch (deviation of 12 degrees). I repeated the calculation with both
B3LYP and BP86 functional and the values are given below:

B3LYP/def2-TZVP   ~ 21.2
BP86/def2-TZVP     ~ 20
Experimental          ~ 8.1

I would not worry too much if it was 2-3 degree deviation, but 12 is something
that I should be careful with.

I was wondering, whether there is a chance for an experimental error? Or is it
just that DFT overestimates the dihedral angle? Does any body know any references
where people encountered similar problem.

I would be thankful for your comments

with kind regards

Gopakumar




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