From owner-chemistry@ccl.net Fri Jan 16 09:34:01 2015 From: "Andreas Klamt klamt]![cosmologic.de" To: CCL Subject: CCL:G: mixed solvent Message-Id: <-50915-150116015521-11541-TgP+mlqmobB3Synu7uIEhQ]*[server.ccl.net> X-Original-From: Andreas Klamt Content-Type: multipart/alternative; boundary="------------070607000709050106090601" Date: Fri, 16 Jan 2015 07:55:14 +0100 MIME-Version: 1.0 Sent to CCL by: Andreas Klamt [klamt-#-cosmologic.de] This is a multi-part message in MIME format. --------------070607000709050106090601 Content-Type: text/plain; charset=utf-8; format=flowed Content-Transfer-Encoding: 8bit Dear Partha, and dear Igors, I am a bit worried about the numbers you distribute: 1) Now first of all, for a mixture you have to specify, whether you consider 1:1 by molfraction or by weight or by volume. 2) For a 1:1 by molfraction mixture of water and methanol I find at 298K a value of ~49, and for 1:1 by weight I find ~56 for epsilon. see e.g. http://link.springer.com/chapter/10.1007%2F978-3-540-75506-7_321#page-1 3) If you have no better information for the dynamic epsilon, then eps_inf = refr. index ² ~ 2 is the best estimate for organic solvents. Igors, where did you get the value of 1??? 4) For mixtures the eps_inf can be reasonably estimated based on volume weighted averaging: eps_inf(x1:x2) = (x1*eps_inf_1*molvol_1+x2*eps_inf_2*molvol_2)/(x1*molvol_1+x2*molvol_2) 5) It is questionable whether a mixture is quantitatively well modelled by just using the mixed eps0 and eps_inf. The non-electrostatic parameters have a non-trivial mixing behaviour. The SMx model seem to have an empirically well working mixing rule for the solvent parameters. COSMO-RS has a theoretical concept, which is completely consistent with respect to mixtures, i.e. it yields thermodynamically (Gibbs-Duhem consistent) free energies. Regards Andreas Am 15.01.2015 um 18:31 schrieb Igors Mihailovs igors.mihailovs0(!)gmail.com: > Dear Partha, > > Gaussian wants from You *_two_* solvent parameters for PCM, _eps_ > (static dielectric constant) and _epsinf_ (dynamic, or optical, > dielectric constant) to be provided in additional input section (after > molecular coordinates table and a blank line). If You do not know the > dynamic one (usually the static is given in textbooks), You may try > using epsinf = 1; this would correspond to very slow relaxation, > capable to describe fully relaxed solvent shell (which has physical > meaning for photon emission or adiabatic ionization / electron > affinity). Or, I have never tried that, You can specify the option > "Dielectric=45.5" instead of "Solvent=Generic", which probably does > the same. > > With best wishes, > Igors Mihailovs (engineer) > Institute of Solid State Physics > University of Latvia > > > 2015-01-15 16:28 GMT+02:00 Partha Sengupta anapspsmo|-|gmail.com > >: > > Friends, I am facing a problem related to using mixed solvent > methanol and water. The 1:1 methanol -water solvent having > dielectric constant 45.5. SCRF(pcm,Solvent=Generic,Read) is not > working in G09W program. Help. > Partha > > -- > Dr. Partha Sarathi Sengupta > Associate Professor > Vivekananda Mahavidyalaya, Burdwan > > -- -------------------- Je suis Charlie! -------------------- -------------------------------------------------- Join us at the 4th-COSMO-RS-Symposium March 2015 http://www.cosmologic.de/symposium.html -------------------------------------------------- Prof. Dr. Andreas Klamt CEO / Geschäftsführer COSMOlogic GmbH & Co. KG Imbacher Weg 46 D-51379 Leverkusen, Germany phone +49-2171-731681 fax +49-2171-731689 e-mail klamt\a/cosmologic.de web www.cosmologic.de [University address: Inst. of Physical and Theoretical Chemistry, University of Regensburg] HRA 20653 Amtsgericht Koeln, GF: Prof. Dr. Andreas Klamt Komplementaer: COSMOlogic Verwaltungs GmbH HRB 49501 Amtsgericht Koeln, GF: Prof. Dr. Andreas Klamt --------------070607000709050106090601 Content-Type: text/html; charset=utf-8 Content-Transfer-Encoding: 8bit
Dear Partha, and dear Igors,

I am a bit worried about the numbers you distribute:
1) Now first of all, for a mixture you have to specify, whether you consider 1:1 by molfraction or by weight or by volume.
2) For a 1:1 by molfraction mixture of water and methanol I find at 298K a value of ~49, and for 1:1 by weight I find ~56 for epsilon.
  see e.g. http://link.springer.com/chapter/10.1007%2F978-3-540-75506-7_321#page-1
3) If you have no better information for the dynamic epsilon, then eps_inf = refr. index ² ~ 2 is the best estimate for organic solvents. Igors, where did you get the value of 1???
4) For mixtures the eps_inf can be reasonably estimated based on volume weighted averaging: eps_inf(x1:x2) = (x1*eps_inf_1*molvol_1+x2*eps_inf_2*molvol_2)/(x1*molvol_1+x2*molvol_2)
5) It is questionable whether a mixture is quantitatively well modelled by just using the mixed eps0 and eps_inf. The non-electrostatic parameters have a non-trivial mixing behaviour.

The SMx model seem to have an empirically well working mixing rule for the solvent parameters. COSMO-RS has a theoretical concept, which is completely consistent with respect to mixtures, i.e. it yields thermodynamically (Gibbs-Duhem consistent) free energies.

Regards

Andreas


Am 15.01.2015 um 18:31 schrieb Igors Mihailovs igors.mihailovs0(!)gmail.com:
Dear Partha,

Gaussian wants from You _two_ solvent parameters for PCM, _eps_ (static dielectric constant) and _epsinf_ (dynamic, or optical, dielectric constant) to be provided in additional input section (after molecular coordinates table and a blank line). If You do not know the dynamic one (usually the static is given in textbooks), You may try using epsinf = 1; this would correspond to very slow relaxation, capable to describe fully relaxed solvent shell (which has physical meaning for photon emission or adiabatic ionization / electron affinity). Or, I have never tried that, You can specify the option "Dielectric=45.5" instead of "Solvent=Generic", which probably does the same.

With best wishes,
Igors Mihailovs (engineer)
Institute of Solid State Physics
University of Latvia


2015-01-15 16:28 GMT+02:00 Partha Sengupta anapspsmo|-|gmail.com <owner-chemistry-$-ccl.net>:
Friends, I am facing a problem related to using mixed solvent methanol and water. The 1:1 methanol -water solvent having dielectric constant 45.5. SCRF(pcm,Solvent=Generic,Read) is not working in G09W program. Help.
Partha

--
Dr. Partha Sarathi Sengupta
Associate Professor
Vivekananda Mahavidyalaya, Burdwan



-- 
--------------------
  Je suis Charlie!
--------------------
--------------------------------------------------
Join us at the 4th-COSMO-RS-Symposium March 2015 
http://www.cosmologic.de/symposium.html
--------------------------------------------------

Prof. Dr. Andreas Klamt
CEO / Geschäftsführer
COSMOlogic GmbH & Co. KG
Imbacher Weg 46
D-51379 Leverkusen, Germany

phone  	+49-2171-731681
fax    	+49-2171-731689
e-mail 	klamt\a/cosmologic.de
web    	www.cosmologic.de

[University address:      Inst. of Physical and
Theoretical Chemistry, University of Regensburg]

HRA 20653 Amtsgericht Koeln, GF: Prof. Dr. Andreas Klamt
Komplementaer: COSMOlogic Verwaltungs GmbH
HRB 49501 Amtsgericht Koeln, GF: Prof. Dr. Andreas Klamt
--------------070607000709050106090601-- From owner-chemistry@ccl.net Fri Jan 16 13:46:01 2015 From: "Igors Mihailovs igors.mihailovs0-$-gmail.com" To: CCL Subject: CCL:G: mixed solvent Message-Id: <-50916-150116115406-31879-Uj266oTDbnzVBMa5T1DEyw|*|server.ccl.net> X-Original-From: Igors Mihailovs Content-Type: multipart/alternative; boundary=001a1134d2e6b8932f050cc7d1ae Date: Fri, 16 Jan 2015 18:53:39 +0200 MIME-Version: 1.0 Sent to CCL by: Igors Mihailovs [igors.mihailovs0.-x-.gmail.com] --001a1134d2e6b8932f050cc7d1ae Content-Type: text/plain; charset=UTF-8 Content-Transfer-Encoding: quoted-printable Dear Dr. Klamt, Thank You very much for this explanation, especially for n**2 ~ 2! Number 1 (vacuum) was conventionally used in our lab to simulate self-solution of organic molecules, and for completely relaxed case it caused no trouble... now, however, I see this conception was quite ridiculous. I had thought about the refractive index after I replied to Partha, but I never supposed to approximate self-solution data with it... Thank You once more! What corresponds to 45.5, I have never checked in any textbook before, just repeated what Partha wrote, but now I actually found out in some older one (of 1983, quite reliable, but hardly accessible out of post-USSR): at 293.15 K they present both values: * eps=3D62.8 * epsinf=3D8.0 These numbers are for mixture with fraction 1:1 by VOLUME. With best wishes, Igors Mihailovs (engineer) Institute of Solid State Physics University of Latvia 2015-01-16 8:55 GMT+02:00 Andreas Klamt klamt]![cosmologic.de < owner-chemistry-x-ccl.net>: > Dear Partha, and dear Igors, > > I am a bit worried about the numbers you distribute: > 1) Now first of all, for a mixture you have to specify, whether you > consider 1:1 by molfraction or by weight or by volume. > 2) For a 1:1 by molfraction mixture of water and methanol I find at 298K = a > value of ~49, and for 1:1 by weight I find ~56 for epsilon. > see e.g. > http://link.springer.com/chapter/10.1007%2F978-3-540-75506-7_321#page-1 > 3) If you have no better information for the dynamic epsilon, then eps_in= f > =3D refr. index =C2=B2 ~ 2 is the best estimate for organic solvents. Igo= rs, where > did you get the value of 1??? > 4) For mixtures the eps_inf can be reasonably estimated based on volume > weighted averaging: eps_inf(x1:x2) =3D > (x1*eps_inf_1*molvol_1+x2*eps_inf_2*molvol_2)/(x1*molvol_1+x2*molvol_2) > 5) It is questionable whether a mixture is quantitatively well modelled b= y > just using the mixed eps0 and eps_inf. The non-electrostatic parameters > have a non-trivial mixing behaviour. > > The SMx model seem to have an empirically well working mixing rule for th= e > solvent parameters. COSMO-RS has a theoretical concept, which is complete= ly > consistent with respect to mixtures, i.e. it yields thermodynamically > (Gibbs-Duhem consistent) free energies. > > Regards > > Andreas > > > Am 15.01.2015 um 18:31 schrieb Igors Mihailovs igors.mihailovs0(!) > gmail.com: > > Dear Partha, > > Gaussian wants from You *_two_* solvent parameters for PCM, _eps_ > (static dielectric constant) and _epsinf_ (dynamic, or optical, dielectri= c > constant) to be provided in additional input section (after molecular > coordinates table and a blank line). If You do not know the dynamic one > (usually the static is given in textbooks), You may try using epsinf =3D = 1; > this would correspond to very slow relaxation, capable to describe fully > relaxed solvent shell (which has physical meaning for photon emission or > adiabatic ionization / electron affinity). Or, I have never tried that, Y= ou > can specify the option "Dielectric=3D45.5" instead of "Solvent=3DGeneric"= , > which probably does the same. > > With best wishes, > Igors Mihailovs (engineer) > Institute of Solid State Physics > University of Latvia > > > 2015-01-15 16:28 GMT+02:00 Partha Sengupta anapspsmo|-|gmail.com < > owner-chemistry-$-ccl.net>: > >> Friends, I am facing a problem related to using mixed solvent methanol >> and water. The 1:1 methanol -water solvent having dielectric constant 45= .5. >> SCRF(pcm,Solvent=3DGeneric,Read) is not working in G09W program. Help. >> Partha >> >> -- >> Dr. Partha Sarathi Sengupta >> Associate Professor >> Vivekananda Mahavidyalaya, Burdwan >> > > > > -- > -------------------- > Je suis Charlie! > -------------------- > -------------------------------------------------- > Join us at the 4th-COSMO-RS-Symposium March 2015 http://www.cosmologic.de= /symposium.html > -------------------------------------------------- > > Prof. Dr. Andreas Klamt > CEO / Gesch=C3=A4ftsf=C3=BChrer > COSMOlogic GmbH & Co. KG > Imbacher Weg 46 > D-51379 Leverkusen, Germany > > phone +49-2171-731681 > fax +49-2171-731689 > e-mail klamt-#-cosmologic.de > web www.cosmologic.de > > [University address: Inst. of Physical and > Theoretical Chemistry, University of Regensburg] > > HRA 20653 Amtsgericht Koeln, GF: Prof. Dr. Andreas Klamt > Komplementaer: COSMOlogic Verwaltungs GmbH > HRB 49501 Amtsgericht Koeln, GF: Prof. Dr. Andreas Klamt > > > > --001a1134d2e6b8932f050cc7d1ae Content-Type: text/html; charset=UTF-8 Content-Transfer-Encoding: quoted-printable
Dear Dr. Klamt,

Thank You very much for this explanation, especially for n**2 ~ 2! Number = 1 (vacuum) was conventionally used in our lab to simulate self-solution of = organic molecules, and for completely relaxed case it caused no trouble... = now, however, I see this conception was quite ridiculous. I had thought abo= ut the refractive index after I replied to Partha, but I never supposed to = approximate self-solution data with it... Thank You once more!

What corresponds to 45.5, I have never checked in any textbook before, jus= t repeated what Partha wrote, but now I actually found out in some older on= e (of 1983, quite reliable, but hardly accessible out of post-USSR):
at 293.15 K they present both values:
* eps=3D62.8
* e= psinf=3D8.0
These numbers are for mixture with fraction 1:1 by VOL= UME.


With best wishes,
Igors Mihai= lovs (engineer)
Institute of Solid State Physics
University of Latvia


2015-01-16 8:55 GMT+02:00 Andreas Klamt klam= t]![cosmologic.de &l= t;owner-chemis= try-x-ccl.net>:
=20 =20 =20
Dear Partha, and dear Igors,

I am a bit worried about the numbers you distribute:
1) Now first of all, for a mixture you have to specify, whether you consider 1:1 by molfraction or by weight or by volume.
2) For a 1:1 by molfraction mixture of water and methanol I find at 298K a value of ~49, and for 1:1 by weight I find ~56 for epsilon.
=C2=A0 see e.g. http://link.springer.com/chapter/10.1007%2= F978-3-540-75506-7_321#page-1
3) If you have no better information for the dynamic epsilon, then eps_inf =3D refr. index =C2=B2 ~ 2 is the best estimate for organic solvents. Igors, where did you get the value of 1???
4) For mixtures the eps_inf can be reasonably estimated based on volume weighted averaging: eps_inf(x1:x2) =3D (x1*eps_inf_1*molvol_1+x2*eps_inf_2*molvol_2)/(x1*molvol_1+x2*molvol_= 2)
5) It is questionable whether a mixture is quantitatively well modelled by just using the mixed eps0 and eps_inf. The non-electrostatic parameters have a non-trivial mixing behaviour.

The SMx model seem to have an empirically well working mixing rule for the solvent parameters. COSMO-RS has a theoretical concept, which is completely consistent with respect to mixtures, i.e. it yields thermodynamically (Gibbs-Duhem consistent) free energies.

Regards

Andreas


Am 15.01.2015 um 18:31 schrieb Igors Mihailovs igors.mihailovs0(!)gma= il.com:
Dear Partha,

Gaussian wants from You _two_ solvent parameters for PCM, _eps_ (static dielectric constant) and _epsinf_ (dynamic, or optical, dielectric constant) to be provided in additional input section (after molecular coordinates table and a blank line). If You do not know the dynamic one (usually the static is given in textbooks), You may try using epsinf =3D 1; this would correspond to very slow relaxation, capable to describe fully relaxed solvent shell (which has physical meaning for photon emission or adiabatic ionization / electron affinity). Or, I have never tried that, You can specify the option "Dielectric=3D45.5" instead of "Solvent=3DGeneric&qu= ot;, which probably does the same.

With best wishes,
Igors Mihailovs (engineer)
Institute of Solid State Physics
University of Latvia


2015-01-15 16:28 GMT+02:00 Partha Sengupta anapspsmo|-|gmail.com <owner-chemistry-$-ccl.net>:
Friends, I am facing a problem related to using mixed solvent methanol and water. The 1:1 methanol -water solvent having dielectric constant 45.5. SCRF(pcm,Solvent=3DGeneric,Read) is not working in G09W program. Help.
Partha

--
Dr. Partha Sarathi Sengupta
Associate Professor
Vivekananda Mahavidyalaya, Burdwan



--=20
--------------------
  Je suis Charlie!
--------------------
--------------------------------------------------
Join us at the 4th-COSMO-RS-Symposium March 2015=20
http:=
//www.cosmologic.de/symposium.html
--------------------------------------------------

Prof. Dr. Andreas Klamt
CEO / Gesch=C3=A4ftsf=C3=BChrer
COSMOlogic GmbH & Co. KG
Imbacher Weg 46
D-51379 Leverkusen, Germany

phone  	+49-2171-731681
fax    	+49-2171-731689
e-mail 	klamt-#-=
cosmologic.de
web    	www.cosmolog=
ic.de

[University address:      Inst. of Physical and
Theoretical Chemistry, University of Regensburg]

HRA 20653 Amtsgericht Koeln, GF: Prof. Dr. Andreas Klamt
Komplementaer: COSMOlogic Verwaltungs GmbH
HRB 49501 Amtsgericht Koeln, GF: Prof. Dr. Andreas Klamt

--001a1134d2e6b8932f050cc7d1ae-- From owner-chemistry@ccl.net Fri Jan 16 14:22:00 2015 From: "Igors Mihailovs igors.mihailovs0!^!gmail.com" To: CCL Subject: CCL:G: mixed solvent Message-Id: <-50917-150116121449-1224-Kc4daQlWlJlsHJZ0iUBPlA*o*server.ccl.net> X-Original-From: Igors Mihailovs Content-Type: multipart/alternative; boundary=089e0158bf4ccd3578050cc81b1e Date: Fri, 16 Jan 2015 19:14:21 +0200 MIME-Version: 1.0 Sent to CCL by: Igors Mihailovs [igors.mihailovs0|gmail.com] --089e0158bf4ccd3578050cc81b1e Content-Type: text/plain; charset=UTF-8 Content-Transfer-Encoding: quoted-printable Mess, I should have thought more carefulll... I apologize, we were able to calculate the VERTICAL ionization for self-solute molecules, because it is epsinf which we can determine from electronic polarizability and volume, calculable in Gaussian... Strangely enough, if I do not mess everything up again, it was usually input as "eps" and "epsinf" was leaved as 1. Should we probably set up eps and epsinf both to the same value? With best wishes, Igors Mihailovs (engineer) Institute of Solid State Physics University of Latvia 2015-01-16 18:53 GMT+02:00 Igors Mihailovs : > Dear Dr. Klamt, > > Thank You very much for this explanation, especially for n**2 ~ 2! Number > 1 (vacuum) was conventionally used in our lab to simulate self-solution o= f > organic molecules, and for completely relaxed case it caused no trouble..= . > now, however, I see this conception was quite ridiculous. I had thought > about the refractive index after I replied to Partha, but I never suppose= d > to approximate self-solution data with it... Thank You once more! > > What corresponds to 45.5, I have never checked in any textbook before, > just repeated what Partha wrote, but now I actually found out in some old= er > one (of 1983, quite reliable, but hardly accessible out of post-USSR): > at 293.15 K they present both values: > * eps=3D62.8 > * epsinf=3D8.0 > These numbers are for mixture with fraction 1:1 by VOLUME. > > > With best wishes, > Igors Mihailovs (engineer) > Institute of Solid State Physics > University of Latvia > > > 2015-01-16 8:55 GMT+02:00 Andreas Klamt klamt]![cosmologic.de < > owner-chemistry*o*ccl.net>: > >> Dear Partha, and dear Igors, >> >> I am a bit worried about the numbers you distribute: >> 1) Now first of all, for a mixture you have to specify, whether you >> consider 1:1 by molfraction or by weight or by volume. >> 2) For a 1:1 by molfraction mixture of water and methanol I find at 298K >> a value of ~49, and for 1:1 by weight I find ~56 for epsilon. >> see e.g. >> http://link.springer.com/chapter/10.1007%2F978-3-540-75506-7_321#page-1 >> 3) If you have no better information for the dynamic epsilon, then >> eps_inf =3D refr. index =C2=B2 ~ 2 is the best estimate for organic solv= ents. >> Igors, where did you get the value of 1??? >> 4) For mixtures the eps_inf can be reasonably estimated based on volume >> weighted averaging: eps_inf(x1:x2) =3D >> (x1*eps_inf_1*molvol_1+x2*eps_inf_2*molvol_2)/(x1*molvol_1+x2*molvol_2) >> 5) It is questionable whether a mixture is quantitatively well modelled >> by just using the mixed eps0 and eps_inf. The non-electrostatic paramete= rs >> have a non-trivial mixing behaviour. >> >> The SMx model seem to have an empirically well working mixing rule for >> the solvent parameters. COSMO-RS has a theoretical concept, which is >> completely consistent with respect to mixtures, i.e. it yields >> thermodynamically (Gibbs-Duhem consistent) free energies. >> >> Regards >> >> Andreas >> >> >> Am 15.01.2015 um 18:31 schrieb Igors Mihailovs igors.mihailovs0(!) >> gmail.com: >> >> Dear Partha, >> >> Gaussian wants from You *_two_* solvent parameters for PCM, _eps_ >> (static dielectric constant) and _epsinf_ (dynamic, or optical, dielectr= ic >> constant) to be provided in additional input section (after molecular >> coordinates table and a blank line). If You do not know the dynamic one >> (usually the static is given in textbooks), You may try using epsinf =3D= 1; >> this would correspond to very slow relaxation, capable to describe fully >> relaxed solvent shell (which has physical meaning for photon emission or >> adiabatic ionization / electron affinity). Or, I have never tried that, = You >> can specify the option "Dielectric=3D45.5" instead of "Solvent=3DGeneric= ", >> which probably does the same. >> >> With best wishes, >> Igors Mihailovs (engineer) >> Institute of Solid State Physics >> University of Latvia >> >> >> 2015-01-15 16:28 GMT+02:00 Partha Sengupta anapspsmo|-|gmail.com < >> owner-chemistry-$-ccl.net>: >> >>> Friends, I am facing a problem related to using mixed solvent methanol >>> and water. The 1:1 methanol -water solvent having dielectric constant 4= 5.5. >>> SCRF(pcm,Solvent=3DGeneric,Read) is not working in G09W program. Help. >>> Partha >>> >>> -- >>> Dr. Partha Sarathi Sengupta >>> Associate Professor >>> Vivekananda Mahavidyalaya, Burdwan >>> >> >> >> >> -- >> -------------------- >> Je suis Charlie! >> -------------------- >> -------------------------------------------------- >> Join us at the 4th-COSMO-RS-Symposium March 2015 http://www.cosmologic.d= e/symposium.html >> -------------------------------------------------- >> >> Prof. Dr. Andreas Klamt >> CEO / Gesch=C3=A4ftsf=C3=BChrer >> COSMOlogic GmbH & Co. KG >> Imbacher Weg 46 >> D-51379 Leverkusen, Germany >> >> phone +49-2171-731681 >> fax +49-2171-731689 >> e-mail klamt-#-cosmologic.de >> web www.cosmologic.de >> >> [University address: Inst. of Physical and >> Theoretical Chemistry, University of Regensburg] >> >> HRA 20653 Amtsgericht Koeln, GF: Prof. Dr. Andreas Klamt >> Komplementaer: COSMOlogic Verwaltungs GmbH >> HRB 49501 Amtsgericht Koeln, GF: Prof. Dr. Andreas Klamt >> >> >> >> > --089e0158bf4ccd3578050cc81b1e Content-Type: text/html; charset=UTF-8 Content-Transfer-Encoding: quoted-printable
Mess, I should have thought more carefulll...
I apologize, we were able to calculate the VERTICAL ionization for self-s= olute molecules, because it is epsinf which we can determine from electroni= c polarizability and volume, calculable in Gaussian... Strangely enough, if= I do not mess everything up again, it was usually input as "eps"= and "epsinf" was leaved as 1. Should we probably set up eps and = epsinf both to the same value?


With best wis= hes,
Igors Mihailovs (engineer)
Institute of Solid St= ate Physics
University of Latvia


2015-01-16 18:53 GMT+02:00 Igors Mihailovs <= span dir=3D"ltr"><igors.mihailovs0*o*gmail.com>:
Dear Dr. Klamt= ,

Thank You very much for this explanation, especially for n**= 2 ~ 2! Number 1 (vacuum) was conventionally used in our lab to simulate sel= f-solution of organic molecules, and for completely relaxed case it caused = no trouble... now, however, I see this conception was quite ridiculous. I h= ad thought about the refractive index after I replied to Partha, but I neve= r supposed to approximate self-solution data with it... Thank You once more= !

What corresponds to 45.5, I have never checked in any textbo= ok before, just repeated what Partha wrote, but now I actually found out in= some older one (of 1983, quite reliable, but hardly accessible out of post= -USSR):
at 293.15 K they present both values:
* eps=3D62.= 8
* epsinf=3D8.0
These numbers are for mixture with fract= ion 1:1 by VOLUME.


With best wishes,
Igors Mi= hailovs (engineer)
Institute of Solid State Physics
=
University of Latvia


2015-01-16 8:5= 5 GMT+02:00 Andreas Klamt klamt]![cosmologic.de <owner-chemistry*o*ccl.net>:
=20 =20 =20
Dear Partha, and dear Igors,

I am a bit worried about the numbers you distribute:
1) Now first of all, for a mixture you have to specify, whether you consider 1:1 by molfraction or by weight or by volume.
2) For a 1:1 by molfraction mixture of water and methanol I find at 298K a value of ~49, and for 1:1 by weight I find ~56 for epsilon.
=C2=A0 see e.g. http://link.springer.com/chapter/10.1007%2= F978-3-540-75506-7_321#page-1
3) If you have no better information for the dynamic epsilon, then eps_inf =3D refr. index =C2=B2 ~ 2 is the best estimate for organic solvents. Igors, where did you get the value of 1???
4) For mixtures the eps_inf can be reasonably estimated based on volume weighted averaging: eps_inf(x1:x2) =3D (x1*eps_inf_1*molvol_1+x2*eps_inf_2*molvol_2)/(x1*molvol_1+x2*molvol_= 2)
5) It is questionable whether a mixture is quantitatively well modelled by just using the mixed eps0 and eps_inf. The non-electrostatic parameters have a non-trivial mixing behaviour.

The SMx model seem to have an empirically well working mixing rule for the solvent parameters. COSMO-RS has a theoretical concept, which is completely consistent with respect to mixtures, i.e. it yields thermodynamically (Gibbs-Duhem consistent) free energies.

Regards

Andreas


Am 15.01.2015 um 18:31 schrieb Igors Mihailovs igors.mihailovs0(!)gma= il.com:
Dear Partha,

Gaussian wants from You _two_ solvent parameters for PCM, _eps_ (static dielectric constant) and _epsinf_ (dynamic, or optical, dielectric constant) to be provided in additional input section (after molecular coordinates table and a blank line). If You do not know the dynamic one (usually the static is given in textbooks), You may try using epsinf =3D 1; this would correspond to very slow relaxation, capable to describe fully relaxed solvent shell (which has physical meaning for photon emission or adiabatic ionization / electron affinity). Or, I have never tried that, You can specify the option "Dielectric=3D45.5" instead of "Solvent=3DGeneric&qu= ot;, which probably does the same.

With best wishes,
Igors Mihailovs (engineer)
Institute of Solid State Physics
University of Latvia


2015-01-15 16:28 GMT+02:00 Partha Sengupta anapspsmo|-|gmail.com <owner-chemistry-$-ccl.net>:
Friends, I am facing a problem related to using mixed solvent methanol and water. The 1:1 methanol -water solvent having dielectric constant 45.5. SCRF(pcm,Solvent=3DGeneric,Read) is not working in G09W program. Help.
Partha

--
Dr. Partha Sarathi Sengupta
Associate Professor
Vivekananda Mahavidyalaya, Burdwan



--=20
--------------------
  Je suis Charlie!
--------------------
--------------------------------------------------
Join us at the 4th-COSMO-RS-Symposium March 2015=20
http:=
//www.cosmologic.de/symposium.html
--------------------------------------------------

Prof. Dr. Andreas Klamt
CEO / Gesch=C3=A4ftsf=C3=BChrer
COSMOlogic GmbH & Co. KG
Imbacher Weg 46
D-51379 Leverkusen, Germany

phone  	+49-2171-731681
fax    	+49-2171-731689
e-mail 	klamt-#-=
cosmologic.de
web    	www.cosmolog=
ic.de

[University address:      Inst. of Physical and
Theoretical Chemistry, University of Regensburg]

HRA 20653 Amtsgericht Koeln, GF: Prof. Dr. Andreas Klamt
Komplementaer: COSMOlogic Verwaltungs GmbH
HRB 49501 Amtsgericht Koeln, GF: Prof. Dr. Andreas Klamt


--089e0158bf4ccd3578050cc81b1e-- From owner-chemistry@ccl.net Fri Jan 16 16:16:01 2015 From: "taki eddine ahmed ARDJANI takiaiman/./yahoo.fr" To: CCL Subject: CCL: How Can I calculate potential energy distribution PED% with VEDA? Message-Id: <-50918-150116161457-17306-CBtLwQUZYgDmNF2RU8WUrA~!~server.ccl.net> X-Original-From: "taki eddine ahmed ARDJANI" Date: Fri, 16 Jan 2015 16:14:56 -0500 Sent to CCL by: "taki eddine ahmed ARDJANI" [takiaiman]-[yahoo.fr] Does somebody know how to calculate PED%, I'd be very grateful if anybody could give me Further information about procedure to calculate PED% with veda programme. I really appreciate any help you can provide From owner-chemistry@ccl.net Fri Jan 16 22:38:00 2015 From: "Andreas Klamt klamt_._cosmologic.de" To: CCL Subject: CCL:G: mixed solvent Message-Id: <-50919-150116180437-9385-ZHHJcmgC3+9rAcbpENCHvg**server.ccl.net> X-Original-From: Andreas Klamt Content-Type: multipart/alternative; boundary="------------090100050200000807060700" Date: Sat, 17 Jan 2015 00:04:29 +0100 MIME-Version: 1.0 Sent to CCL by: Andreas Klamt [klamt/a\cosmologic.de] This is a multi-part message in MIME format. --------------090100050200000807060700 Content-Type: text/plain; charset=utf-8; format=flowed Content-Transfer-Encoding: 8bit Igors, sorry, but eps_inf=8 is nonsense. There is no liquid with such hign eps_inf in this world. For non-polar solvents eps0=eps_inf=n² is a good approximation. Otherwise eps is much larger than eps_inf. Regards Andreas Am 16.01.2015 um 18:14 schrieb Igors Mihailovs igors.mihailovs0!^!gmail.com: > Mess, I should have thought more carefulll... > I apologize, we were able to calculate the VERTICAL ionization for > self-solute molecules, because it is epsinf which we can determine > from electronic polarizability and volume, calculable in Gaussian... > Strangely enough, if I do not mess everything up again, it was usually > input as "eps" and "epsinf" was leaved as 1. Should we probably set up > eps and epsinf both to the same value? > > > With best wishes, > Igors Mihailovs (engineer) > Institute of Solid State Physics > University of Latvia > > > 2015-01-16 18:53 GMT+02:00 Igors Mihailovs gmail.com >: > > Dear Dr. Klamt, > > Thank You very much for this explanation, especially for n**2 ~ 2! > Number 1 (vacuum) was conventionally used in our lab to simulate > self-solution of organic molecules, and for completely relaxed > case it caused no trouble... now, however, I see this conception > was quite ridiculous. I had thought about the refractive index > after I replied to Partha, but I never supposed to approximate > self-solution data with it... Thank You once more! > > What corresponds to 45.5, I have never checked in any textbook > before, just repeated what Partha wrote, but now I actually found > out in some older one (of 1983, quite reliable, but hardly > accessible out of post-USSR): > at 293.15 K they present both values: > * eps=62.8 > * epsinf=8.0 > These numbers are for mixture with fraction 1:1 by VOLUME. > > > With best wishes, > Igors Mihailovs (engineer) > Institute of Solid State Physics > University of Latvia > > > 2015-01-16 8:55 GMT+02:00 Andreas Klamt klamt]![cosmologic.de > >: > > Dear Partha, and dear Igors, > > I am a bit worried about the numbers you distribute: > 1) Now first of all, for a mixture you have to specify, > whether you consider 1:1 by molfraction or by weight or by > volume. > 2) For a 1:1 by molfraction mixture of water and methanol I > find at 298K a value of ~49, and for 1:1 by weight I find ~56 > for epsilon. > see e.g. > http://link.springer.com/chapter/10.1007%2F978-3-540-75506-7_321#page-1 > 3) If you have no better information for the dynamic epsilon, > then eps_inf = refr. index ² ~ 2 is the best estimate for > organic solvents. Igors, where did you get the value of 1??? > 4) For mixtures the eps_inf can be reasonably estimated based > on volume weighted averaging: eps_inf(x1:x2) = > (x1*eps_inf_1*molvol_1+x2*eps_inf_2*molvol_2)/(x1*molvol_1+x2*molvol_2) > 5) It is questionable whether a mixture is quantitatively well > modelled by just using the mixed eps0 and eps_inf. The > non-electrostatic parameters have a non-trivial mixing behaviour. > > The SMx model seem to have an empirically well working mixing > rule for the solvent parameters. COSMO-RS has a theoretical > concept, which is completely consistent with respect to > mixtures, i.e. it yields thermodynamically (Gibbs-Duhem > consistent) free energies. > > Regards > > Andreas > > > Am 15.01.2015 um 18:31 schrieb Igors Mihailovs > igors.mihailovs0(!)gmail.com : >> Dear Partha, >> >> Gaussian wants from You *_two_* solvent parameters for PCM, >> _eps_ (static dielectric constant) and _epsinf_ (dynamic, or >> optical, dielectric constant) to be provided in additional >> input section (after molecular coordinates table and a blank >> line). If You do not know the dynamic one (usually the static >> is given in textbooks), You may try using epsinf = 1; this >> would correspond to very slow relaxation, capable to describe >> fully relaxed solvent shell (which has physical meaning for >> photon emission or adiabatic ionization / electron affinity). >> Or, I have never tried that, You can specify the option >> "Dielectric=45.5" instead of "Solvent=Generic", which >> probably does the same. >> >> With best wishes, >> Igors Mihailovs (engineer) >> Institute of Solid State Physics >> University of Latvia >> >> >> 2015-01-15 16:28 GMT+02:00 Partha Sengupta >> anapspsmo|-|gmail.com >> >: >> >> Friends, I am facing a problem related to using mixed >> solvent methanol and water. The 1:1 methanol -water >> solvent having dielectric constant 45.5. >> SCRF(pcm,Solvent=Generic,Read) is not working in G09W >> program. Help. >> Partha >> >> -- >> Dr. Partha Sarathi Sengupta >> Associate Professor >> Vivekananda Mahavidyalaya, Burdwan >> >> > > > -- > -------------------- > Je suis Charlie! > -------------------- > -------------------------------------------------- > Join us at the 4th-COSMO-RS-Symposium March 2015 > http://www.cosmologic.de/symposium.html > -------------------------------------------------- > > Prof. Dr. Andreas Klamt > CEO / Geschäftsführer > COSMOlogic GmbH & Co. KG > Imbacher Weg 46 > D-51379 Leverkusen, Germany > > phone +49-2171-731681 > fax +49-2171-731689 > e-mail klamt-#-cosmologic.de > web www.cosmologic.de > > [University address: Inst. of Physical and > Theoretical Chemistry, University of Regensburg] > > HRA 20653 Amtsgericht Koeln, GF: Prof. Dr. Andreas Klamt > Komplementaer: COSMOlogic Verwaltungs GmbH > HRB 49501 Amtsgericht Koeln, GF: Prof. Dr. Andreas Klamt > > > > -- -------------------- Je suis Charlie! -------------------- -------------------------------------------------- Join us at the 4th-COSMO-RS-Symposium March 2015 http://www.cosmologic.de/symposium.html -------------------------------------------------- Prof. Dr. Andreas Klamt CEO / Geschäftsführer COSMOlogic GmbH & Co. KG Imbacher Weg 46 D-51379 Leverkusen, Germany phone +49-2171-731681 fax +49-2171-731689 e-mail klamt[#]cosmologic.de web www.cosmologic.de [University address: Inst. of Physical and Theoretical Chemistry, University of Regensburg] HRA 20653 Amtsgericht Koeln, GF: Prof. Dr. Andreas Klamt Komplementaer: COSMOlogic Verwaltungs GmbH HRB 49501 Amtsgericht Koeln, GF: Prof. Dr. Andreas Klamt --------------090100050200000807060700 Content-Type: text/html; charset=utf-8 Content-Transfer-Encoding: 8bit
Igors,

sorry, but eps_inf=8 is nonsense. There is no liquid with such hign eps_inf in this world.

For non-polar solvents eps0=eps_inf=n² is a good approximation. Otherwise eps is much larger than eps_inf.

Regards

Andreas

Am 16.01.2015 um 18:14 schrieb Igors Mihailovs igors.mihailovs0!^!gmail.com:
Mess, I should have thought more carefulll...
I apologize, we were able to calculate the VERTICAL ionization for self-solute molecules, because it is epsinf which we can determine from electronic polarizability and volume, calculable in Gaussian... Strangely enough, if I do not mess everything up again, it was usually input as "eps" and "epsinf" was leaved as 1. Should we probably set up eps and epsinf both to the same value?


With best wishes,
Igors Mihailovs (engineer)
Institute of Solid State Physics
University of Latvia


2015-01-16 18:53 GMT+02:00 Igors Mihailovs <igors.mihailovs0 ~~ gmail.com>:
Dear Dr. Klamt,

Thank You very much for this explanation, especially for n**2 ~ 2! Number 1 (vacuum) was conventionally used in our lab to simulate self-solution of organic molecules, and for completely relaxed case it caused no trouble... now, however, I see this conception was quite ridiculous. I had thought about the refractive index after I replied to Partha, but I never supposed to approximate self-solution data with it... Thank You once more!

What corresponds to 45.5, I have never checked in any textbook before, just repeated what Partha wrote, but now I actually found out in some older one (of 1983, quite reliable, but hardly accessible out of post-USSR):
at 293.15 K they present both values:
* eps=62.8
* epsinf=8.0
These numbers are for mixture with fraction 1:1 by VOLUME.


With best wishes,
Igors Mihailovs (engineer)
Institute of Solid State Physics
University of Latvia
2015-01-16 8:55 GMT+02:00 Andreas Klamt klamt]![cosmologic.de <owner-chemistry ~~ ccl.net>:
Dear Partha, and dear Igors,

I am a bit worried about the numbers you distribute:
1) Now first of all, for a mixture you have to specify, whether you consider 1:1 by molfraction or by weight or by volume.
2) For a 1:1 by molfraction mixture of water and methanol I find at 298K a value of ~49, and for 1:1 by weight I find ~56 for epsilon.
  see e.g. http://link.springer.com/chapter/10.1007%2F978-3-540-75506-7_321#page-1
3) If you have no better information for the dynamic epsilon, then eps_inf = refr. index ² ~ 2 is the best estimate for organic solvents. Igors, where did you get the value of 1???
4) For mixtures the eps_inf can be reasonably estimated based on volume weighted averaging: eps_inf(x1:x2) = (x1*eps_inf_1*molvol_1+x2*eps_inf_2*molvol_2)/(x1*molvol_1+x2*molvol_2)
5) It is questionable whether a mixture is quantitatively well modelled by just using the mixed eps0 and eps_inf. The non-electrostatic parameters have a non-trivial mixing behaviour.

The SMx model seem to have an empirically well working mixing rule for the solvent parameters. COSMO-RS has a theoretical concept, which is completely consistent with respect to mixtures, i.e. it yields thermodynamically (Gibbs-Duhem consistent) free energies.

Regards

Andreas


Am 15.01.2015 um 18:31 schrieb Igors Mihailovs igors.mihailovs0(!)gmail.com:
Dear Partha,

Gaussian wants from You _two_ solvent parameters for PCM, _eps_ (static dielectric constant) and _epsinf_ (dynamic, or optical, dielectric constant) to be provided in additional input section (after molecular coordinates table and a blank line). If You do not know the dynamic one (usually the static is given in textbooks), You may try using epsinf = 1; this would correspond to very slow relaxation, capable to describe fully relaxed solvent shell (which has physical meaning for photon emission or adiabatic ionization / electron affinity). Or, I have never tried that, You can specify the option "Dielectric=45.5" instead of "Solvent=Generic", which probably does the same.

With best wishes,
Igors Mihailovs (engineer)
Institute of Solid State Physics
University of Latvia


2015-01-15 16:28 GMT+02:00 Partha Sengupta anapspsmo|-|gmail.com <owner-chemistry-$-ccl.net>:
Friends, I am facing a problem related to using mixed solvent methanol and water. The 1:1 methanol -water solvent having dielectric constant 45.5. SCRF(pcm,Solvent=Generic,Read) is not working in G09W program. Help.
Partha

--
Dr. Partha Sarathi Sengupta
Associate Professor
Vivekananda Mahavidyalaya, Burdwan



-- 
--------------------
  Je suis Charlie!
--------------------
--------------------------------------------------
Join us at the 4th-COSMO-RS-Symposium March 2015 
http://www.cosmologic.de/symposium.html
--------------------------------------------------

Prof. Dr. Andreas Klamt
CEO / Geschäftsführer
COSMOlogic GmbH & Co. KG
Imbacher Weg 46
D-51379 Leverkusen, Germany

phone  	+49-2171-731681
fax    	+49-2171-731689
e-mail 	klamt-#-cosmologic.de
web    	www.cosmologic.de

[University address:      Inst. of Physical and
Theoretical Chemistry, University of Regensburg]

HRA 20653 Amtsgericht Koeln, GF: Prof. Dr. Andreas Klamt
Komplementaer: COSMOlogic Verwaltungs GmbH
HRB 49501 Amtsgericht Koeln, GF: Prof. Dr. Andreas Klamt







-- 
--------------------
  Je suis Charlie!
--------------------
--------------------------------------------------
Join us at the 4th-COSMO-RS-Symposium March 2015 
http://www.cosmologic.de/symposium.html
--------------------------------------------------

Prof. Dr. Andreas Klamt
CEO / Geschäftsführer
COSMOlogic GmbH & Co. KG
Imbacher Weg 46
D-51379 Leverkusen, Germany

phone  	+49-2171-731681
fax    	+49-2171-731689
e-mail 	klamt[#]cosmologic.de
web    	www.cosmologic.de

[University address:      Inst. of Physical and
Theoretical Chemistry, University of Regensburg]

HRA 20653 Amtsgericht Koeln, GF: Prof. Dr. Andreas Klamt
Komplementaer: COSMOlogic Verwaltungs GmbH
HRB 49501 Amtsgericht Koeln, GF: Prof. Dr. Andreas Klamt
--------------090100050200000807060700--