Firefly and PC GAMESS-related discussion club

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Alexandr
planfactor@mail.ru

>> What will it give to me?
>Imagine you have a diatomic molecule. You probably know, that the minimum energy is found in a Morse potential (http://en.wikipedia.org/wiki/Morse_potentialhttp://en.wikipedia.org/wiki/Morse_potentialhttp://en.wikipedia.org/wiki/Morse_potentialhttp://en.wikipedia.org/wiki/Morse_potential). The Morse potential can be approximated as a harmonic oscillator around the minimum (http://en.wikipedia.org/wiki/Quantum_harmonic_oscillatorhttp://en.wikipedia.org/wiki/Quantum_harmonic_oscillatorhttp://en.wikipedia.org/wiki/Quantum_harmonic_oscillatorhttp://en.wikipedia.org/wiki/Quantum_harmonic_oscillator). If you regard a harmonic oscillator with quantum mechanical equations you'll find out, that the Molecule can never reach the minimum of your curve. The difference between the lowest possible state and the minimum of your PES-curve is the zero point energy. �
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>>Perhaps, it is necessary to correct received for them TOTAL ENERGY?
>If you compare energies you often compare your TOTAL ENERGYs and your corrected TOTAL ENERGYs, where you added the zero point energy. Note, that your TOTAL ENERGY is always negative, while your zero point energy is positive, so you get:
>-1311.5429273+0.280207=-1311.26272

>Your corrected total energies should be considered to be more precise than the not corrected ones, but always remember that the zero point energy is approximated.

>hope this helps,

>Fabian
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>On Thu Jan 20 '11 0:15am, Alexandr wrote
>----------------------------------------
>>Hi,

>>I perform work with a molecule of organic connection from 40 atoms.
>>In the beginning I find a stationary point:

>>$contrl=optimize [.]
>>[...]

>>... I receive:
>>[...]
>>ENERGY =-1311.5429273
>>[...]
>>MAXIMUM GRADIENT = 0.0000744 RMS GRADIENT = 0.0000248
>>1 ***** EQUILIBRIUM GEOMETRY LOCATED *****
>>[...]

>>Further for the found stationary point I calculate hessian:
>>$contrl=hessian [...]
>>[...]
>> �� � � � � � � � � � ��1 � � � �2 � � � 3 � � �4 � � �5
>> � � � FREQUENCY: � �36.36 � �32.43 � 10.77 � 8.51 � 5.90 �
>> � �REDUCED MASS: � 8.77061 8.84577 9.28704 8.91738 9.52289
>> � �IR INTENSITY: � 0.18500 0.10810 0.05133 0.12040 0.03344
>>[...}
>>Thank God, all frequencies are positive, hence, the found stationary point
>>characterises a minimum (local) on PES.
>>But further I read in thermodynamics section:
>>[...}
>> THE HARMONIC ZERO POINT ENERGY IS (SCALED BY 1.000)
>> � � � �0.280207 HARTREE/MOLECULE
>>[...}
>>How to use this size 0.280207? To take away, add to size TOTAL ENERGY received above?
>> What will it give to me? I count a series from this and ionic forms.
>>Perhaps, it is necessary to correct received for them TOTAL ENERGY?
>>I wait for the help.

>>With regards,
>>Alexandr
>>

Hi, Fabian and clubmen FireFly!

Thanks for excursion in the quantum mechanics. But I still had number of the doubts, concerning
practical use THE HARMONIC ZERO POINT ENERGY:

1. Why this energy on a scale (SCALED BY 1.000)?
Whether it means, what number 0.280207 is a share of unit? And what then it is taken for unit?
Really -1311.5429273? Then your algebraic addition does not work.

2. I so understand that those who uses this amendment, spend calculations for ideal gas. So it is
possible to calculate authors of articles who do it, but article text do not admit. It is a shame
to them, as their processes go in real, more often water environments. And in the water environment
as I already have found out practically with use FireFly, differ and very much!
  Then, if I do PCM-optimise, PCM-tddft, PCM-hessian in the water environment ($PCM solvnt=H2O)
this ZERO-amendment is not necessary to me?

  What your opinion and clubmen FireFly?

With regards,

Alexandr