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【转载】高斯中溶剂模型没有相应溶剂的解决办法[zz]
CCL:G: Dioxane in PCM with G03
--------------------------------------------------------------------------------
From: Madi
Subject: CCL:G: Dioxane in PCM with G03
Date: Thu, 14 May 2009 17:17:29 -0400
--------------------------------------------------------------------------------
Sent to CCL by: Madi [madi7sk{:}gmail.com]
Hi,
I was trying to specify DMF using the PCM model in gaussian and was
having trouble
getting it to work. I wrote to gaussian and their reply was very
helpful. I am attaching it
here for your reference. After you are done specifying all the
parameters, make sure
you deliberately leave a blank line.
Hope this helps
madi
******************************************************************
Regarding the specification of the DMF solvent, even though only the
solvents listed in the Gaussian documentation of the SCRF keyword are
available through the "Solvent=" option, a different solvent may be
explicitly defined in the PCM input. However, please, note that it is
not possible to input all parameters that define an arbitrary solvent.
Specifically, one cannot define all of the terms necessary to
calculate the non-electrostatic contributions. For this reason, there
are two recommended alternatives:
1) Check in the list of solvents provided for the SCRF keyword whether
there is a solvent similar enough to the one you would like to use in
your calculation and provide this name in the "Solvent" option of the
SCRF keyword. Then, add also the "Read" option to provide the
modifications of "EPS", "RSOLV", "Density", and
"VMOL". This way, you
would be introducing the parameters for your desired solvent, for the
cases of parameters that are available for user input, and the program
would be using the closest possible parameters for those other
parameters that are not available for user input. (Note: if no solvent
is specified, then the program defaults to water). So, probably, your
best choice here would be to select a solvent with similar properties
to DMF (such as Acetonitrile, DMSO, Acetone, Nitromethane) and then
give the corresponding "EPS", "RSOLV", "Density",
and "VMOL"
parameters for DMF.
2) Alternatively, you can use the options "NoDis NoRep NoCav" in order
to prevent the use of the parameters for the internally stored solvent
(water, by default), so the non-electrostatic contributions to the
solvation energy will not be computed. Note also that this is true if
the default "UA0" radii are used, the electrostatic terms are then
correctly computed this way. If this is not the case, and the UAHF or
UAKS radii are used, then there is a dependency of the radius with the
type of solvent so it would not be correct to use a modified water as
a model for a solvent with properties different than water. Thus, if
UAHF or UAKS radii are used, then one has to still do what it was
explained in the previous paragraph, 1), (that is to use the
"Solvent=" option to select, from the list of predefined solvents, a
solvent similar to the one you are interested in).
For the calculation of only the electrostatic part, you can define the
solvent by defining the dielectric constant using the "EPS" option,
the solvent radius using the "RSOLV" option, and the dielectric
constant at infinite frequency using the "EPSINF". EPSINF is the
dielectric constant at infinite frequency. It is an experimentally
measured value. The value of EPSINF will not affect the results of
ground-state energy calculation of DeltaG(solv), so you do not need to
worry about getting a non-standard value. EPSINF is only necessary
when performing excited state PCM calculations. Other than EPS, RSOLV
usually makes the biggest difference in the result. As for choosing a
value of RSOLV, our developers recommended a couple of references they
use for this parameter:
* O. Sinanoglu in "Molecular Interactions" Z. Ratajczack and
Orville-Thomas eds, Wiley 1982 vol. 3 chap. 6
* M.H. Abraham and A. Nasehzadeh J. Chem. Soc. Faraday Trans. 1 1981, 77, 340.
If the desired RSOLV parameter is not found there, the molar volume
may give some hints for RSOLV values for new solvents, even though
attention must be paid to the chemical nature of the solvent, because
strong interactions modify, to some extent, the definition of the hard
sphere analogue of the solvent molecular volume. Thus, although a
simple approximation, the Stearn-Eyring formula (Stearn, Eyring J.
Chem. Phys. 1937, 5, 113) can be used to derive a value for RSOLV,
given the molar volume of the solvent.
Finally, about other parameters, which only affect the
non-electrostatic terms, the DENSITY is a "number density", i.e.
number of particles per volume, and the units are Angstroms^–3. Taking
the density of the solvent in "g * cm^–3", divide by the molar
weight
of the solvent and multiply by Avogadro's number to transform the
grams into number of particles, and, finally, divide by 10^24 to
transform cm^–3 into Angstrom^–3.
Although the density and the molar volume are obviously related, these
two quantities are used by the program to compute two different energy
contributions and, unfortunately, they were introduced in the code as
two independent parameters. Thus, the user needs to provide both the
density ("DENSITY" PCM keyword) and the molar volume ("VMOL"
PCM
keyword) in order to set the desired modifications, so the two of them
are consistent with each other. The units of the density are
Angstrom^–3 while the units of the molar volume are cm^3. So, from the
value of the density of the solvent in "g * cm^–3", take the
inverse
of the density and then divide by the molar weight of the solvent in
order to get the molar volume in cm^3. Enter this parameter in your
input file with the "VMOL" PCM keyword.
The following input will use the standard parameters for the solvent
given in "Solvent=", and modify those given in the
additional
PCM options (the values given below are not representative of any
particular solvent and they are only given as an example of how to use
these keywords):
%
#P SCRF=(PCM,Solvent=,READ) /
<br />
<Charge Multiplicity><br />
<Coordinates><br />
EPS=6.0<br />
RSOLV=1.6<br />
DENSITY=0.045<br />
VMOL=19.05<br />
<br />
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支持，很有用的 </td>
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悠悠天地，奈何独立苍茫？ </div>
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Good!!!! </td>
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<font color=red><b>★ ★ ★ </b></font><br>小木虫(金币<b>+0.5</b>):给个红包，谢谢回帖交流<br>yjcmwgk(金币+2): 2010-03-24 19:08 </div>
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怎么理解“take the<br />
inverse<br />
of the density and then divide by the molar weight of the solvent in<br />
order to get the molar volume in cm^3.”<br />
似乎有点问题啊 </td>
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<div class="pls_info"><span class="xmc_fr"><a href="/t-1808723-1-pid-4#pid4" onclick="setCopy(this.href);return false;">4楼</a></span><em class="xmc_c9">2010-01-27 15:59:47 </em></div>
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<a href="space.php?uid=942214" >haifeng-quan</a>
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<p class="xmc_c6"><a href="membertop.php">金虫</a> (初入文坛)</p> <p class="forum_Star"><em style=" width:72px"></em></p>
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讲的很清楚，谢谢！ </td>
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