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bur2000

Germany
36 Posts

Posted - 12/09/2013 :  03:58:41 AM  Show Profile  Edit Topic  Reply with Quote  View user's IP address  Delete Topic
In Origin 8.6 the following function is used for Boltzmann Fit:

y = A2 + (A1-A2)/(1 + exp((x-x0)/dx))

I never heard about this function in connection with Boltzmann. Actually, this function is what is generally called Boltzmann:

y = A2 + (A1-A2)/(1 + exp(-E/k*x))

Both functions are sigmoidal, but it's not possible to create the exact same curve with both of them.

I assume the Origin Boltzmann Fit returns the inflection point = x0 of the curve but has no physical meaning? And the "real" Boltzmann returns the activation energy = E? Is there any specific reason why Origin uses this special function instead of normal Boltzmann?

Edited by - bur2000 on 12/09/2013 04:01:37 AM

Hideo Fujii

USA
1582 Posts

Posted - 12/11/2013 :  12:02:26 PM  Show Profile  Edit Reply  Reply with Quote  View user's IP address  Delete Reply
[quote][i]Originally posted by bur2000

> Both functions are sigmoidal...
> Is there any specific reason why Origin uses this special function instead of normal Boltzmann?

You have cited:
(1) y = A2 + (A1-A2)/(1 + exp((x-x0)/dx))  (in Origin)
(2) y = A2 + (A1-A2)/(1 + exp(-E/k*x))   (the function you called "real" Boltzmann)
Your (2) is not sigmoidal. Though physical Boltzmann function usually regards the temperature as the independent variable, the sigmoidal version should regard the T as a parameter, and E is the independent variable. (I guess that this kind of interpretation may be more common in the Boltzmann machine in the machine learning - x as the mere input, y as the output.).)
Therefore, it should be expressed as:
(2)' y(E) = A2 + (A1-A2)/(1 + exp(-E/k*T))
Origin as a general-purpose software, the formula has taken a more general form, I think, such as introducing the offsets of x and y. So, as k*T = -dx, you can get the temperature from Origin's formula by T=-dx/k .
Of course, k is the Boltzmann constant in physics, but can have various different meanings in other applications.

I'm not a physicist, and this is just what I thought.

--Hideo Fujii
OriginLab

P.S. When you fit your data with Boltzmann in Origin, if you need to set e.g., x0 to 0 as in your model, you can fix the parameter to 0 by entering 0 to the Value field, and turning ON the "Fixed" check box in the Parameter tab in NLFit tool.

P.P.S. You can define a derived parameter T in the Boltzmann's function definition in the Fitting Function Organizer (even though this is a built-in function) such as T=-dx/1.38E-23 .

Edited by - Hideo Fujii on 12/11/2013 1:20:44 PM
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bur2000

Germany
36 Posts

Posted - 12/17/2013 :  03:04:34 AM  Show Profile  Edit Reply  Reply with Quote  View user's IP address  Delete Reply
Thanks for your reply, that makes sense to me.
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