On Aug 2, 2011, at 8:18 AM, mohaddeseh abbasnejad wrote:

> Dear Prof. Baroni
>  
> Thanks again
>> Dear Prof. Baroni
>>  
>> Thanks for your reply.
>> I wonder shouldn't the plot show the same frequency for a range of 
>> displacements?
> 
> what range? why should it?
> 
> 
> -- Because if we are in the neighberhood of a minimum "where a quadratic 
> could be fitted", any displacement in that range should result the same 
> frequency. By displacement, I mean the same pattern but different in 
> amplitude.

who said this? around a minimum, the only thing you can say is that the Taylor 
expansion of the energy in powers of the atomic displacements lacks any linear 
terms. In general, it has both quadratic terms (which are the one you are 
interested in), as well as higher order terms ... No reason why the Taylor 
expansion should be *exactly* quadratic (which is what would give rise to a 
"same frequency"). Note however, that it is your definition of frequency that 
is probably flawed. I suspect that you define the frequency as the ratio 
between the energy variation and the square of the displacement, which 
obviously depends on the magnitude of the displacement, if the energy variation 
is not exactly quadratic. The correct definition, instead, is the *limit* of 
that ration when the displacement goes to zero. That limit is obviously well 
defined, independently of the magnitude of any particular distortion that you 
may consider.

>  
>> And the same freq. for the range to be the harmonic frequency? or the zero 
>> displacement limit, is the harmonic frequency?
> 
> yes, by definition

See the above discussion

> 
>> And when I test the displacements with the same amplitude, but different in 
>> sign (regarding the inward and outward atomic movements in the basis) I do 
>> not get the same results.
> 
> why should you?
> 
>> Shouldn't the plot have symmetry vs. the vertical axis?
> 
> why?
> 
> -- Consider for example a linear chain of atoms, with 2 atoms per basis. The 
> optical mode is the result of the outward movement of the atoms (The one in 
> +a/2 moves towards +x and the one in -a/2 moves towards -x). I expect that if 
> I displace the atoms in an inward movement with the same amplitude as the 
> outward, I should see the same frequency (The one in +a/2 moves towards -x 
> and the one in -a/2 moves towards +x) because the 2 patterns present the same 
> mode, right? That is what I've done in the case of Diamond. Is my expectation 
> wrong?

Yes. If the Taylor expansion of the energy difference vs displacement has cubic 
terms (as it usually has, but in very special cases dictated by symmetry), 
there is no reason why the energy difference should be even with respect to 
energy displacement. Actually, it usually isn't ...

Hope this clarifies a bit the situation ...

Take care
SB

---
Stefano Baroni - SISSA  &  DEMOCRITOS National Simulation Center - Trieste
http://stefano.baroni.me [+39] 040 3787 406 (tel) -528 (fax) / stefanobaroni 
(skype)

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