CCL:G: Binding Enthalpy in vacuum and solvent



Dear CCG1
You can use SCFVAC (in G03) or DOVACUMM (in G09) options in SCRF  to calculate delta G solvation energy directly in one calculation. This option performs one calculation in gas phase.
Note: these options are defined by "read" card in SCRF.
Sincerely;
M. Ibrahim


2010/5/14 CompChem Group compchemgroup1 _ gmail.com <owner-chemistry ~~ ccl.net>
Dear Professor Ahmed El-Nahas and all
Thanks for reply. According to IUPAC, the defination of solvation energy is "The change in Gibbs energy when an ion or molecule is transferred from a vacuum (or the gas phase) to a solvent. The main contributions to the solvation energy come from: (a) the cavitation energy of formation of the hole which preserves the dissolved species in the solvent; (b) the orientation energy of partial orientation of the dipoles; (c) the isotropic interaction energy of electrostatic and dispersion origin; and (d) the anisotropic energy of specific interactions, e.g. hydrogen bonds, donor-acceptor interactions etc."
However, I calculated Ni2+ cation in water, please see this part of output:

Variational PCM results
 =======================
 <psi(f)|   H    |psi(f)>                     (a.u.) =   -1507.146446
 <psi(f)|H+V(f)/2|psi(f)>                     (a.u.) =   -1507.887943
 Total free energy in solution:
  with all non electrostatic terms            (a.u.) =   -1507.882504
 --------------------------------------------------------------------
 (Polarized solute)-Solvent               (kcal/mol) =    -465.30
 --------------------------------------------------------------------
 Cavitation energy                        (kcal/mol) =       3.41
 Dispersion energy                        (kcal/mol) =       0.00
 Repulsion energy                         (kcal/mol) =       0.00
 Total non electrostatic                  (kcal/mol) =       3.41
--------------------------------------------------------------------

Did you mean by solvation energy the highlight one?
Thanks,
CCG1

بتاريخ 13 مايو, 2010 05:08 ص، جاء من Ahmed El-Nahas amelnahas!=!hotmail.com <owner-chemistry^_^ccl.net>:
 
People add solvent (in term of PCM) to the reactants and products; the solvation of bar metal ions releases a lot of kcal/mols at the expense of the total reaction enthalpy. If you look at the energy of solvation of the ligand, metal ion and complex, separately, you will realize this fact. I have a similar situation with a difference of about 150-300 kcal/mol between gas phase and solution, depending of your metal ion, ligand and the resulting complex.
 

 
=============================
Professor Ahmed El-Nahas
Physical Chemistry (Quantum Chemistry)
Computational Chemistry Unit (CCU)
Chemistry Department
Faculty of Science
El-Menoufia University
Shebin El-Kom
Egypt
Email: amelnahas:_:http://hotmail.com" target="_blank">hotmail.com
Tel: +2-016-4607974; +81-09062124377
==============================



 
> From: owner-chemistry:_:ccl.net
> To: amelnahas:_:hotmail.com
> Subject: CCL: Binding Enthalpy in vacuum and solvent
> Date: Wed, 12 May 2010 09:29:15 -0400
>
>
> Sent to CCL by: "Comp Chem Group " [compchemgroup1 a gmail.com]
> Dear All,
> By surveying on "Interaction Enthalpy" of transition metal complex in vacuum and solvent (PCM or other model), I found in all cases that the enthalpy change in vacuum is larger than that solvent. For example, if delta H in vacuum= -1000 kcal/mol, in solvent= -200 kcal/mol. Could anyone explain why?
> Regards,
> CCG1
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