CCL: Thermodynamic Data & Solvation - Calculation Questions:
- From: MIELCZAREK Detlev Conrad
- Subject: CCL: Thermodynamic Data & Solvation - Calculation
- Date: Thu, 6 Apr 2017 06:24:59 +0000
Sent to CCL by: MIELCZAREK Detlev Conrad [detlev-conrad.mielczarek]^[ifpen.fr]
Dear CCL, a question on thermodynamic data & solvation from me, maybe you
can help me.
So, the basic problem for me is, that I am calculating/want to calculate
thermodynamic data (Hf, S - hence also dG) in solvation, using implicit
solvation models, SMD with a COSMO cavity to be specific. For my application,
these should be accurate enough. (So no molecular dynamics simulations etc.)
Solvation models are normally parametrised for dGsolv - so this value can be
extracted from the quantum chemistry calculation as the difference in the
calculated Gibbs Free Enthalpy.
Hf can calculated easily in the gas phase, and a re-optimisation of the
structure with solvation should capture the majority of the impact of solvation
on the enthalpy. (Which is dominated by molecular structure.)
(I guess there is the case of stabilisation and complexes, such as are reported
for water. However this is currently beyond the scope of my work.)
The topic of solvation has been discussed previously on the CCL here:
And there is the book "Essentials of Computational Chemistry Theories and
Models" from Professor Cramer with a section on phase change (the source of
Specifically, the discussion concerning the energy change related to the state
conversion causes me some grief.
On the one hand, the CCL responses read as if this should be applied in the case
of any phase change, but then others suggest this is applicable only if the
process is a second order reaction and thus the total number of mols changes? -
The latter view seems to agree with the book...
So if I have compound A in both the gas and liquid phase (from a quantum
chemistry calculation), do I need to account for the phase change/change of
state or not? Or is it something that can be included in the parametrisation of
the solvation model/the quantum chemistry code already?
Just to add more confusion to the topic: I have trialled a commercial product
which gives the Gibbs Enthalpy of Solvation in kcal/mol for mol/L concentrations
and using a very low end/fast functional, it gives values similar to when a
correction term is added... on the other hand, where available, the calculated
values without correction agree with the published values in the SMD paper: http://pubs.acs.org/doi/abs/10.1021/jp810292n (Supplementary
In addition, a regular computational chemistry calculation sees very little
(virtually no) difference in the entropy between the gaseous and solvated phase.
This would agree with the CCL-linked paper here http://pubs.acs.org/doi/abs/10.1021/jp205508z . But this
would clash with the common expectation that entropy in the liquid phase is
Hence, I would highly appreciate if someone knowledgeable in the field of
solvation could guide me onto the correct track.
Detlev Conrad Mielczarek
Scientific Visitor/Post Doctorant
IFP Energies nouvelles
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