From owner-chemistry@ccl.net Thu Dec 2 07:45:00 2010 From: "Wilhelm Eger eger!^!theochem.tu-muenchen.de" To: CCL Subject: CCL:G: Uncontracted basis sets for NMR calculations in Gaussian Message-Id: <-43256-101202065259-16628-VxV0YL/sSDo0RGSNXfnwGg . server.ccl.net> X-Original-From: "Wilhelm Eger" Date: Thu, 2 Dec 2010 06:52:56 -0500 Sent to CCL by: "Wilhelm Eger" [eger..theochem.tu-muenchen.de] Dear all, as mentioned in the subject, I would like to use uncontracted basis sets in Gaussian to enhance the accuracy of NMR predictions. Further information about this topic can be found in: Deng, J. Chem. Theory Comput., 2006, 2, 1028 The authors suggest to use an uncontracted aug-cc-pVTZ 'augmented by the number of s functions found to be sufficient to saturate the core region'. My system is pretty large and consists of hydrogens, carbon, and oxygen atoms as well as two zinc ions. The question is: How to use uncontracted basis sets in Gaussian? Do I need to: - download a special basis set from EMSL (I didn't find one, though) - use the provided aug-cc-pVTZ and some special keywords (e. g. UnconAOBasis or UnconDBF)? Thanks in advance, Wilhelm From owner-chemistry@ccl.net Thu Dec 2 08:20:00 2010 From: "fatemeh moosavi fatemeh.moosavi .. gmail.com" To: CCL Subject: CCL:G: keyword GEN for iodide anion Message-Id: <-43257-101202071617-22795-WDkPbahUhko+qyysdXN49g*server.ccl.net> X-Original-From: fatemeh moosavi Content-Type: text/plain; charset=ISO-8859-1 Date: Thu, 2 Dec 2010 04:16:08 -0800 MIME-Version: 1.0 Sent to CCL by: fatemeh moosavi [fatemeh.moosavi|a|gmail.com] Dear Abu Asaduzzaman Thanks a million for your suggestion. My job has been run. Best wishes F. Moosavi On 12/1/10, nijamudheen a apchnijam:_:gmail.com wrote: > Dear Fatemeh Moosavi, > > go through this link > http://wanglab.bu.edu/g03guide/G03Guide/www.gaussian.com/g_ur/k_pseudo.htm > See the sample input given below > > > %chk=tfa_complex_int.chk > %mem=200MW > # opt freq rb3lyp/gen pseudo=read > > Title Card Required > > 0 1 > Au 1.25702900 0.02768900 -0.48637900 > N 2.23605600 1.79959000 -0.10315500 > N -0.33935200 1.07801500 -1.25122900 > N 0.33990400 -1.74142400 -1.00845800 > N 2.91983800 -1.02228900 0.13359500 > C 1.72912000 3.07752300 -0.31843800 > C 3.49680700 1.92955300 0.46875700 > C -0.95180700 -1.87081900 -1.50640800 > C 0.85456100 -3.01923700 -0.82171800 > C -0.47153600 2.46083600 -1.28324000 > C -1.53006300 0.52672200 -1.71189700 > C 4.07985000 -0.47340200 0.66909500 > C 3.05810000 -2.40710600 0.14072700 > C 2.71245700 4.04350000 0.12976400 > H -0.84476200 2.08339900 2.22861300 > C -0.15688500 -0.01816900 1.94211800 > C -0.70368500 -1.24313700 2.58133900 > H -0.00389300 -1.88455800 3.12311200 > H -1.33811300 -1.79789600 1.87319900 > C -5.19145000 0.05268300 0.08222700 > F -6.38947500 -0.50583400 0.54700000 > F -5.44430000 1.42040400 -0.12666300 > F -5.00129300 -0.48199000 -1.21934100 > C -3.97698100 -0.21356200 1.05691600 > O -3.17409900 -1.13361800 0.68338400 > O -3.97901600 0.54246000 2.08477800 > > H C N O F 0 > 6-31+g(d,p) > **** > Au 0 > lanl2dz > **** > > Au 0 > lanl2dz > > > > > > On Thu, Dec 2, 2010 at 12:11 AM, Abu Asaduzzaman a.asaduzzaman##gmail.com < > owner-chemistry*ccl.net> wrote: > >> Just remove the first four stars (****) after the geometry specification. >> >> On Wed, Dec 1, 2010 at 11:02 AM, Fatemeh Moosavi fatemeh.moosavi/./ >> gmail.com wrote: >> >>> >>> Sent to CCL by: "Fatemeh Moosavi" [fatemeh.moosavi[*]gmail.com] >>> Deal all >>> I have run the optimization job for a series of imidazolium based ionic >>> liquids having iodide as anion. Since the basis set 6-311g** cannot be >>> applied to I, I had to use the gen keyword with basis set extra input. >>> Now, I need to run the same job for anion I (I-). However, there is the >>> problem and I cannot solve it. >>> In the output, I get this massage: >>> Last state="Top" >>> TCursr= 879 LCursr= 0 >>> Error reading general basis specification. >>> Error termination via Lnk1e in C:\G03W\l301.exe at Sun Nov 14 22:47:10 >>> 2010. >>> Job cpu time: 0 days 0 hours 0 minutes 5.0 seconds. >>> File lengths (MBytes): RWF= 11 Int= 0 D2E= 0 Chk= 1 >>> Scr= 1 >>> >>> My input file is: >>> %chk=Ig.chk >>> %mem=6MW >>> # b3lyp/gen opt freq >>> >>> Title Card Required >>> >>> -1 1 >>> I >>> >>> 1 >>> >>> **** >>> I 0 >>> S 5 1.00 >>> 444750.0000000 0.0008900 >>> 66127.0000000 0.0069400 >>> 14815.0000000 0.0360900 >>> 4144.9000000 0.1356800 >>> 1361.2000000 0.3387800 >>> S 2 1.00 >>> 508.4400000 0.4365900 >>> 209.5900000 0.1837500 >>> S 1 1.00 >>> 81.9590000 1.0000000 >>> S 1 1.00 >>> 36.8050000 1.0000000 >>> S 1 1.00 >>> 13.4950000 1.0000000 >>> S 1 1.00 >>> 6.8859000 1.0000000 >>> S 1 1.00 >>> 2.5520000 1.0000000 >>> S 1 1.00 >>> 1.2088000 1.0000000 >>> S 1 1.00 >>> 0.2734000 1.0000000 >>> S 1 1.00 >>> 0.1009000 1.0000000 >>> P 4 1.00 >>> 2953.6000000 0.0122100 >>> 712.6100000 0.0858700 >>> 236.7100000 0.2949300 >>> 92.6310000 0.4784900 >>> P 1 1.00 >>> 39.7320000 1.0000000 >>> P 1 1.00 >>> 17.2730000 1.0000000 >>> P 1 1.00 >>> 7.9570000 1.0000000 >>> P 1 1.00 >>> 3.1529000 1.0000000 >>> P 1 1.00 >>> 1.3328000 1.0000000 >>> P 1 1.00 >>> 0.4947000 1.0000000 >>> P 1 1.00 >>> 0.2160000 1.0000000 >>> P 1 1.00 >>> 0.0829300 1.0000000 >>> D 3 1.00 >>> 261.9500000 0.0314400 >>> 76.7340000 0.1902800 >>> 27.5510000 0.4724700 >>> D 1 1.00 >>> 10.6060000 1.0000000 >>> D 1 1.00 >>> 3.4217000 1.0000000 >>> D 1 1.00 >>> 1.1370000 1.0000000 >>> D 1 1.00 >>> 0.3020000 1.0000000 >>> **** >>> >>> Would any one please advise me to be able run this job successfully? >>> >>> Great appreciation for the suggestions and thanks in advance >>> >>> Best regards >>> F. Moosavi >>> PhD student in Physical Chemistry >>> Department of Chemistry >>> Shiraz University >>> Shiraz, 71454 >>> Iran >>> fatemeh.moosavi .. gmail.com>> E-mail to subscribers: CHEMISTRY:+:ccl.net >>> or use:>> >>> E-mail to administrators: CHEMISTRY-REQUEST:+:ccl.net or use>> >>> >>> >> > > > -- > With Best Regards, > > ************************************ > NIJAMUDHEEN. A > PROJECT FELLOW > IISER, THIRUVANANTHAPURAM-695016 > INDIA. > PH: 91-9995642629 > EMAIL: apchnijam*gmail.com > ************************************* > > Every move is a treasure to be spent for the best reasons - Svetozar > Gligoric > From owner-chemistry@ccl.net Thu Dec 2 08:55:00 2010 From: "Sayed Mesa elsayed.elmes**yahoo.com" To: CCL Subject: CCL:G: Is the ferromagentic state = the triplet state? Message-Id: <-43258-101202084324-17468-gcBULQW4u9dGY6wybvSv0A(-)server.ccl.net> X-Original-From: "Sayed Mesa" Date: Thu, 2 Dec 2010 08:43:21 -0500 Sent to CCL by: "Sayed Mesa" [elsayed.elmes[#]yahoo.com] Dear CCL community, I am calculating dinuclear copper (II) complex using B3LYP/Mixed basis set (Gaussian 09). This means each Cu(II)has one unpaired electron (d9). I have calculated the different spin states: (1)singlet state (2)Triplet state (3)Antiferromagentic state (where spin of one unpaired electron is alpha, and the other is beta) I found that the Antiferromagentic state is the lowest energy. My question is the ferromagentic spin state is the triplet one? or I should calculate the ferromagentic state by fragmenting the spin of Cu-atoms into alpha and alpha (As I mentioned in the case for Antiferromagentic state ) Regards, Sayed From owner-chemistry@ccl.net Thu Dec 2 09:30:00 2010 From: "Ol Ga eurisco1---pochta.ru" To: CCL Subject: CCL:G: Uncontracted basis sets for NMR calculations in Gaussian Message-Id: <-43259-101202085003-24044-c7YHq2x+tZmx3E9r2fj8rA*_*server.ccl.net> X-Original-From: "Ol Ga" Date: Thu, 2 Dec 2010 08:49:59 -0500 Sent to CCL by: "Ol Ga" [eurisco1() pochta.ru] Dear Wilhelm Eger, I would suggest you to use (aug)-cc-pVxZ-J (very suitable for SSCC calculation and can be applied for shielding constant calculations), (aug)-cc-p(w)CVxZ, aug-pcS-n and aug-pcJ-n. All the basis set are available https://bse.pnl.gov/bse/portal. They are balanced, forms hierarchy and are exactly what you need for SSCC and shielding constants calculation. Sincerely, Ol Ga ----- ----- > From: Wilhelm Eger eger!^!theochem.tu-muenchen.de Sent: Thursday, December 02, 2010 2:52 PM To: Ga, Ol Subject: CCL:G: Uncontracted basis sets for NMR calculations in Gaussian Sent to CCL by: "Wilhelm Eger" [eger..theochem.tu-muenchen.de] Dear all, as mentioned in the subject, I would like to use uncontracted basis sets in Gaussian to enhance the accuracy of NMR predictions. Further information about this topic can be found in: Deng, J. Chem. Theory Comput., 2006, 2, 1028 The authors suggest to use an uncontracted aug-cc-pVTZ 'augmented by the number of s functions found to be sufficient to saturate the core region'. My system is pretty large and consists of hydrogens, carbon, and oxygen atoms as well as two zinc ions. The question is: How to use uncontracted basis sets in Gaussian? Do I need to: - download a special basis set from EMSL (I didn't find one, though) - use the provided aug-cc-pVTZ and some special keywords (e. g. UnconAOBasis or UnconDBF)? Thanks in advance, Wilhelm From owner-chemistry@ccl.net Thu Dec 2 10:05:01 2010 From: "Tanja van Mourik tanja.vanmourik*st-andrews.ac.uk" To: CCL Subject: CCL:G: Uncontracted basis sets for NMR calculations in Gaussian Message-Id: <-43260-101202092241-24900-cbLXTd1yHGWmheX/nmW3rA##server.ccl.net> X-Original-From: Tanja van Mourik Content-Transfer-Encoding: 7bit Content-Type: text/plain; charset=ISO-8859-1; format=flowed Date: Thu, 02 Dec 2010 14:21:18 +0000 MIME-Version: 1.0 Sent to CCL by: Tanja van Mourik [tanja.vanmourik/./st-andrews.ac.uk] Dear Wilhelm, > as mentioned in the subject, I would like to use uncontracted basis sets in Gaussian to enhance the accuracy of NMR predictions. > > Further information about this topic can be found in: > > Deng, J. Chem. Theory Comput., 2006, 2, 1028 > > The authors suggest to use an uncontracted aug-cc-pVTZ 'augmented by the number of s functions found to be sufficient to saturate the core region'. > > My system is pretty large and consists of hydrogens, carbon, and oxygen atoms as well as two zinc ions. > > The question is: How to use uncontracted basis sets in Gaussian? The quoted paper also mentions that the proposed scheme to modify basis sets for the calculation of spin-spin couplings has been implemented in Gaussian (version 03, revision D), see the end of section 5 in the paper by Deng et al. Basically, you need to use NMR=Mixed. Note that the basis set modification is only done for the calculation of the Fermi-Contact term of the couplings; the other three Ramsay terms are calculated with the unmodified basis set. Best wishes, Tanja -- ================================================================ Tanja van Mourik Senior Lecturer in Chemistry School of Chemistry, University of St. Andrews North Haugh, St. Andrews, Fife KY16 9ST, Scotland (UK) email: tanja.vanmourik|-|st-andrews.ac.uk web: http://chemistry.st-and.ac.uk/staffmember.php?id=tvm The University of St Andrews is a charity registered in Scotland: No SC013532 ================================================================ From owner-chemistry@ccl.net Thu Dec 2 10:40:00 2010 From: "Johannes Johansson johjo76..gmail.com" To: CCL Subject: CCL: Is the ferromagentic state = the triplet state? Message-Id: <-43261-101202102410-24032-qs7eJe5ZisnjNn415rTyoA/./server.ccl.net> X-Original-From: Johannes Johansson Content-Type: multipart/alternative; boundary=0016363b8f20d01c6704966f0272 Date: Thu, 2 Dec 2010 16:23:59 +0100 MIME-Version: 1.0 Sent to CCL by: Johannes Johansson [johjo76*gmail.com] --0016363b8f20d01c6704966f0272 Content-Type: text/plain; charset=UTF-8 Dear Sayed, is the spin population ~1alfa on both Cu atoms in the triplet state and ~1alfa and ~1beta on the Cu-atoms in the open-shell singlet state? If so, then these are the ferro- and antiferromagnetically coupled states respectively. A closed-shell singlet state of this system requires disproportionation to a Cu(I)-Cu(III) oxidation state. Best regards / Johannes -- Adam Johannes Johansson Ph.D., M.Sc. Division of Physical Chemistry KTH (Royal Institute of Technology) Teknikringen 36 SE-100 44 Stockholm Sweden Office: 087908217 Cell phone: 0708178487 E-mail:johjo76 ~ gmail.com Research web page:www.physto.se/~johjo --0016363b8f20d01c6704966f0272 Content-Type: text/html; charset=UTF-8 Content-Transfer-Encoding: quoted-printable Dear Sayed,

is the spin population ~1alfa on both Cu ato= ms in the triplet state and ~1alfa and ~1beta on the Cu-atoms in the open-s= hell singlet state? If so, then these are the ferro- and antiferromagnetica= lly coupled states respectively. A closed-shell singlet state of this syste= m requires disproportionation to a Cu(I)-Cu(III) oxidation state.

Best regards / Johannes=C2=A0

--
Adam Johannes Johansson
Ph.D., M.Sc.
Div= ision of Physical Chemistry
KTH (Royal Institute of Technology)
Tekni= kringen 36
SE-100 44 Stockholm
Sweden
Office: 087908217
Cell phone: 0708178487
E-mail:johjo76 ~ gmail.com
Research web page:www.physto.se/~johjo
--0016363b8f20d01c6704966f0272-- From owner-chemistry@ccl.net Thu Dec 2 12:03:00 2010 From: "may abdelghani may01dz{}yahoo.fr" To: CCL Subject: CCL: the relativistic effect ... after or before the geometry optimization Message-Id: <-43262-101202114630-31326-SrDyitp2sii3Q6yep9sacA+/-server.ccl.net> X-Original-From: may abdelghani Content-Type: multipart/alternative; boundary="0-1073316016-1291308377=:66588" Date: Thu, 2 Dec 2010 16:46:17 +0000 (GMT) MIME-Version: 1.0 Sent to CCL by: may abdelghani [may01dz|yahoo.fr] --0-1073316016-1291308377=:66588 Content-Type: text/plain; charset=iso-8859-1 Content-Transfer-Encoding: quoted-printable Hello, =0A=0A=0AIt is recommended to=0Aconsidered (or add) the relativistic effect= (with ZORA for example) to your=0Acalculation after or before the geometry= optimization procedure:filtered #yiv1872785688 {margin:2cm;}=0A#yiv1872785= 688 P {margin-bottom:0.21cm;}=0A-->=0A=0Aa Non-relativistic geometry optimi= zation followed by a single point=0Arelativistic calculation??? may abdelghani=09Laboratoire de chimie des mat=E9riaux et des vivants: Acti= vit=E9, R=E9activit=E9 =0A=0A=0A --0-1073316016-1291308377=:66588 Content-Type: text/html; charset=iso-8859-1 Content-Transfer-Encoding: quoted-printable
Hello,
=0A

It is r= ecommended to=0Aconsidered (or add) the relativistic effect (with ZORA for = example) to your=0Acalculation after or before the geometry optimization pr= ocedure=0A

a Non-relativistic geometry optimiza= tion followed by a single point=0Arelativistic calculation???=




may abdelghani=09
Laboratoire de chimie des mat=E9ria= ux et des vivants: Activit=E9, R=E9activit=E9

=0A=0A=0A=0A=0A --0-1073316016-1291308377=:66588-- From owner-chemistry@ccl.net Thu Dec 2 16:03:00 2010 From: "elsayed elmeselhy elsayed.elmes]-[yahoo.com" To: CCL Subject: CCL: Is the ferromagentic state = the triplet state? Message-Id: <-43263-101202153735-23711-CYzgr1Ti9+9hEWkqGsqkwA::server.ccl.net> X-Original-From: elsayed elmeselhy Content-Type: multipart/alternative; boundary="0-671658696-1291322246=:20996" Date: Thu, 2 Dec 2010 12:37:26 -0800 (PST) MIME-Version: 1.0 Sent to CCL by: elsayed elmeselhy [elsayed.elmes*yahoo.com] --0-671658696-1291322246=:20996 Content-Type: text/plain; charset=iso-8859-1 Content-Transfer-Encoding: quoted-printable Dear Dr. Adam, Thanks for your response. I would be appreciated if you clarified the follo= wing points: 1- "A closed-shell singlet state of this system requires disproportionation= to a Cu(I)-Cu(III) oxidation state." My system is [Cu2L]4+ where L is macrocyclic ligand. Both copper cations ha= ve oxidation state =3D +2. Could you explain me how and why the calculation= of a closed-shell singlet state of my system=A0 leads to disproportionatio= n to a Cu(I)-Cu(III) oxidation state. If there is a publication(s) refer to= that please, let me know. 2- is the spin population ~1alfa on both Cu atoms in the triplet state and = =0A~1alfa and ~1beta on the Cu-atoms in the open-shell singlet state? Did you mean to say open-shell triplet state=A0 (~1alfa on both Cu atoms) a= nd open-shell singlet state (~1alfa and ~1beta on the Cu-atoms), respective= ly?=20 In the first case, there are two alpha for Cu2+, then it should be=A0 open = shell triplet state: In other word, in the input file, we should fragment= =A0 the multiplicities of the molecule as the following: 3 :the=A0 multiplicity for whole complex (because the number of unpaired el= etrons =3D 2) 2 : the multiplicity for the first Cu(2+) (because the number of unpaired e= letrons =3D1) 2 : the multiplicity for the second Cu(2+) (because the number of unpaired = eletrons =3D 1) 1: the multiplicity for ligand (because the number of unpaired eletrons =3D= 0) Please let me know your opinion asap. Regards, Sayed --- On Thu, 12/2/10, Johannes Johansson johjo76..gmail.com wrote: > From: Johannes Johansson johjo76..gmail.com Subject: CCL: Is the ferromagentic state =3D the triplet state? To: "Mesa, Sayed " Date: Thursday, December 2, 2010, 5:23 PM Dear Sayed, is the spin population ~1alfa on both Cu atoms in the triplet state and ~1a= lfa and ~1beta on the Cu-atoms in the open-shell singlet state? If so, then= these are the ferro- and antiferromagnetically coupled states respectively= . A closed-shell singlet state of this system requires disproportionation t= o a Cu(I)-Cu(III) oxidation state.=0A Best regards / Johannes=A0 --=20 Adam Johannes Johansson Ph.D., M.Sc. Division of Physical Chemistry KTH (Royal Institute of Technology) Teknikringen 36 =0ASE-100 44 Stockholm Sweden Office: 087908217 =0ACell phone: 0708178487 E-mail:johjo76||gmail.com Research web page:www.physto.se/~johjo =0A=0A=0A=0A=0A --0-671658696-1291322246=:20996 Content-Type: text/html; charset=iso-8859-1 Content-Transfer-Encoding: quoted-printable
Dear Dr. Adam,

Thanks for your respons= e. I would be appreciated if you clarified the following points:
1- "A closed-shell singlet state of th= is system requires disproportionation to a Cu(I)-Cu(III) oxidation state."

My system is [Cu2L]4+ where L is macrocyclic ligand. Both cop= per cations have oxidation state =3D +2. Could you explain me how and why t= he calculation of a closed-shell singlet state of my system  leads to disproportionation to a = Cu(I)-Cu(III) oxidation state. If there is a publication(s) refer to that p= lease, let me know.

2- i= s the spin population ~1alfa on both Cu atoms in the triplet state and =0A~= 1alfa and ~1beta on the Cu-atoms in the open-shell singlet state?
Did you mean to say open-shell triplet state  (~1alfa on both Cu atoms) and open-shell si= nglet state (~1alfa and ~1beta = on the Cu-atoms), respectively?

In the first case, there are= two alpha for Cu2+, then it should be  open shell triplet state: In o= ther word, in the input file, we should fragment  the multiplicities o= f the molecule as the following:
3 :the  multiplicity for whole com= plex (because the number of unpaired eletrons =3D 2)
2 : the multiplicit= y for the first Cu(2+) (because the number of unpaired eletrons =3D1)
2 = : the multiplicity for the second Cu(2+) (because the number of unpaired el= etrons =3D 1)
1: the multiplicity for ligand (because the number of unpa= ired eletrons =3D0)

Please let me know your opinion asap.

Regards,
Sayed

--- On Thu, 12/2/10, Johannes Joh= ansson johjo76..gmail.com <owner-chemistry() ccl.net> wrote:=

From: Johannes Johansson johjo76..gmail.co= m <owner-chemistry() ccl.net>
Subject: CCL: Is the ferromagentic sta= te =3D the triplet state?
To: "Mesa, Sayed " <elsayed.elmes() y= ahoo.com>
Date: Thursday, December 2, 2010, 5:23 PM

Dear Sayed,

is the spin population ~1alf= a on both Cu atoms in the triplet state and ~1alfa and ~1beta on the Cu-ato= ms in the open-shell singlet state? If so, then these are the ferro- and an= tiferromagnetically coupled states respectively. A closed-shell singlet sta= te of this system requires disproportionation to a Cu(I)-Cu(III) oxidation = state.
=0A

Best regards / Johannes 
=

--
Adam Johannes Joha= nsson
Ph.D., M.Sc.
Division of Physical Chemistry
KTH (Royal Insti= tute of Technology)
Teknikringen 36
=0ASE-100 44 Stockholm
Sweden<= br>Office: 087908217
=0ACell phone: 0708178487
E-mail:johjo76||gmail.com=
Research web page:www.physto.se/~johjo
=0A
=0A

=0A=0A=0A=0A=0A=0A=0A=0A --0-671658696-1291322246=:20996-- From owner-chemistry@ccl.net Thu Dec 2 19:09:00 2010 From: "Johannes Johansson johjo76,gmail.com" To: CCL Subject: CCL:G: Is the ferromagentic state = the triplet state? Message-Id: <-43264-101202190347-16470-8S3XaAaEF0PUM/xF6GO80g-$-server.ccl.net> X-Original-From: Johannes Johansson Content-Type: multipart/alternative; boundary=00163630f835521c610496764575 Date: Fri, 3 Dec 2010 01:03:40 +0100 MIME-Version: 1.0 Sent to CCL by: Johannes Johansson [johjo76|a|gmail.com] --00163630f835521c610496764575 Content-Type: text/plain; charset=UTF-8 Dear Sayed, I give my answers below. Sincerely / Johannes 2010/12/2 elsayed elmeselhy elsayed.elmes]-[yahoo.com < owner-chemistry#%#ccl.net> > Dear Dr. Adam, > > Thanks for your response. I would be appreciated if you clarified the > following points: > 1- "A closed-shell singlet state of this system requires > disproportionation to a Cu(I)-Cu(III) oxidation state." > > My system is [Cu2L]4+ where L is macrocyclic ligand. Both copper cations > have oxidation state = +2. Could you explain me how and why the calculation > of a closed-shell singlet state of my system leads to disproportionation > to a Cu(I)-Cu(III) oxidation state. If there is a publication(s) refer to > that please, let me know. > > I was a bit too fast here. Does your system have a direct Cu-Cu bond? If so, then I guess a closed-shell singlet state is possible even if both ions are in oxidation states with odd number of electrons. (I was thinking about systems in which there is no direct bond between the copper ions, e.g. Cu-O-O-Cu, which can not have a closed-shell singlet state with zero spin on both Cu-atoms if these are Cu(II) since it is an odd number ion (d9). In such systems, the only possibility to get a closed-shell singlet state is if the Cu(II)/Cu(II) oxidation state disproportionates to Cu(I)/Cu(III), most likely a high energy state.) Is there any experimental data available for your system? Maybe for a similar system? Here is an exp ref for a bio-mimetic Cu(II)-O-O-Cu(II) complex, which has an antiferromagnetic ground state: *Karlin et al, JACS, 1993, 115, 2677*. Karlin and co-workers have done a lot of exp work on Cu-dimers so there might be more interesting papers for you in his work. > 2- is the spin population ~1alfa on both Cu atoms in the triplet state and > ~1alfa and ~1beta on the Cu-atoms in the open-shell singlet state? > > Did you mean to say open-shell triplet state (~1alfa on both Cu atoms) > and open-shell singlet state (~1alfa and ~1beta on the Cu-atoms), > respectively? > > Yes (a triplet state is always open-shell). In the first case, there are two alpha for Cu2+, then it should be open > shell triplet state: In other word, in the input file, we should fragment > the multiplicities of the molecule as the following: > 3 :the multiplicity for whole complex (because the number of unpaired > eletrons = 2) > 2 : the multiplicity for the first Cu(2+) (because the number of unpaired > eletrons =1) > 2 : the multiplicity for the second Cu(2+) (because the number of unpaired > eletrons = 1) > 1: the multiplicity for ligand (because the number of unpaired eletrons =0) > > Yes, but to get the triplet state M=3 should be enough. To get the corresponding antiferromagnetic coupling, these specifications might be necessary but then with M=1 for the system as a whole. (I have not done this with Gaussian but is very easy with Jaguar or Turbomole.) Good luck! / Johannes > Please let me know your opinion asap. > > Regards, > Sayed > > --- On *Thu, 12/2/10, Johannes Johansson johjo76..gmail.com > * wrote: > > > From: Johannes Johansson johjo76..gmail.com > Subject: CCL: Is the ferromagentic state = the triplet state? > To: "Mesa, Sayed " > Date: Thursday, December 2, 2010, 5:23 PM > > > Dear Sayed, > > is the spin population ~1alfa on both Cu atoms in the triplet state and > ~1alfa and ~1beta on the Cu-atoms in the open-shell singlet state? If so, > then these are the ferro- and antiferromagnetically coupled states > respectively. A closed-shell singlet state of this system requires > disproportionation to a Cu(I)-Cu(III) oxidation state. > > Best regards / Johannes > > -- > Adam Johannes Johansson > Ph.D., M.Sc. > Division of Physical Chemistry > KTH (Royal Institute of Technology) > Teknikringen 36 > SE-100 44 Stockholm > Sweden > Office: 087908217 > Cell phone: 0708178487 > E-mail:johjo76||gmail.com > Research web page:www.physto.se/~johjo > > > -- Adam Johannes Johansson Ph.D., M.Sc. Division of Physical Chemistry KTH (Royal Institute of Technology) Teknikringen 36 SE-100 44 Stockholm Sweden Office: 087908217 Cell phone: 0708178487 E-mail:johjo76#%#gmail.com Research web page:www.physto.se/~johjo --00163630f835521c610496764575 Content-Type: text/html; charset=UTF-8 Content-Transfer-Encoding: quoted-printable Dear Sayed,

I give my answers below.

Sincerely / Johannes

2010/12/2 elsa= yed elmeselhy elsayed.elmes]-[yahoo.com <owner-chemis= try#%#ccl.net>
Dear Dr. = Adam,

Thanks for your response. I would be appreciated if you clarified the follo= wing points:
1- "A closed= -shell singlet state of this system requires disproportionation to a Cu(I)-= Cu(III) oxidation state."

My system is [Cu2L]4+ where L is macrocyclic ligand. Both copper cation= s have oxidation state =3D +2. Could you explain me how and why the calcula= tion of a closed-shell singlet state of my system=C2=A0 leads to disproportionation to a Cu(I)-Cu(III= ) oxidation state. If there is a publication(s) refer to that please, let m= e know.

I was a bit too fast here. = Does your system have a direct Cu-Cu bond? If so, then I guess a closed-she= ll singlet state is possible even if both ions are in oxidation states with= odd number of electrons. (I was thinking about systems in which there is n= o direct bond between the copper ions, e.g. Cu-O-O-Cu, which can not have a= closed-shell singlet state with zero spin on both Cu-atoms if these are Cu= (II) since it is an odd number ion (d9). In such systems, the only possibil= ity to get a closed-shell singlet state is if the Cu(II)/Cu(II) oxidation s= tate disproportionates to Cu(I)/Cu(III), most likely a high energy state.)<= /div>

Is there any experimental data available for your syste= m? Maybe for a similar system? Here is an exp ref for a bio-mimetic Cu(II)-= O-O-Cu(II) complex, which has an antiferromagnetic ground state:=C2=A0Ka= rlin et al, JACS, 1993, 115, 2677. Karlin and co-workers have done a lo= t of exp work on Cu-dimers so there might be more interesting papers for yo= u in his work.

=C2=A0
<= /tbody>
2- is the spin population ~1alfa = on both Cu atoms in the triplet state and=20 ~1alfa and ~1beta on the Cu-atoms in the open-shell singlet state?
=C2=A0
Did you mean to say open-shell triplet state=C2=A0 (~1alfa on both Cu atoms) and open-shell singlet s= tate (~1alfa and ~1beta on the Cu= -atoms), respectively?

Yes (a triplet state is alw= ays open-shell).

In the first case, the= re are two alpha for Cu2+, then it should be=C2=A0 open shell triplet state= : In other word, in the input file, we should fragment=C2=A0 the multiplici= ties of the molecule as the following:
3 :the=C2=A0 multiplicity for whole complex (because the number of unpaired= eletrons =3D 2)
2 : the multiplicity for the first Cu(2+) (because the = number of unpaired eletrons =3D1)
2 : the multiplicity for the second Cu= (2+) (because the number of unpaired eletrons =3D 1)
1: the multiplicity for ligand (because the number of unpaired eletrons =3D= 0)

Yes, but to get the t= riplet state M=3D3 should be enough. To get the corresponding antiferromagn= etic coupling, these specifications might be necessary but then with M=3D1 = for the system as a whole. (I have not done this with Gaussian but is very = easy with Jaguar or Turbomole.)

Good luck! / Johannes
=C2=A0
Please let me know your opinion asap.

Regards,
Sayed

--- On Thu, 12/2/10, Johannes Joh= ansson johjo76..gmail.com <owner-chemistry-,-ccl= .net> wrote:

From: Johannes Johansson johjo76..gmail.com <owner-chemistry-,-ccl.net>
Subject: CCL: Is the ferromagentic state =3D the triplet state?
To: &quo= t;Mesa, Sayed " <elsayed.elmes-,-yahoo.com>
Date: Thursday, December 2, 2010, 5:23 PM=


Dear Sayed,

is= the spin population ~1alfa on both Cu atoms in the triplet state and ~1alf= a and ~1beta on the Cu-atoms in the open-shell singlet state? If so, then t= hese are the ferro- and antiferromagnetically coupled states respectively. = A closed-shell singlet state of this system requires disproportionation to = a Cu(I)-Cu(III) oxidation state.

Best regards / Johannes=C2=A0

= --
Adam Johannes Johansson
Ph.D., M.Sc.
Division of Physical Chem= istry
KTH (Royal Institute of Technology)
Teknikringen 36
SE-100 44 Stockholm
Sweden
Office: 087908217
Cell phone: 0708178487
E-mail:johjo76||gmail.com=
Research web page:www.physto.se/~johjo




--
Adam Johannes Joh= ansson
Ph.D., M.Sc.
Division of Physical Chemistry
KTH (Royal Inst= itute of Technology)
Teknikringen 36
SE-100 44 Stockholm
Sweden Office: 087908217
Cell phone: 0708178487
E-mail:johjo76#%#gmail.com
Research web page:www.physto.se/~johjo
--00163630f835521c610496764575-- From owner-chemistry@ccl.net Thu Dec 2 22:56:00 2010 From: "Li qiang cougarhead_2003||yahoo.com" To: CCL Subject: CCL:G: a question regarding TS finding in g03 Message-Id: <-43265-101202225001-5980-HSWboc7Wh0V/WCo+cpJP2Q]_[server.ccl.net> X-Original-From: Li qiang Content-Type: multipart/alternative; boundary="0-690508305-1291348194=:20547" Date: Thu, 2 Dec 2010 19:49:54 -0800 (PST) MIME-Version: 1.0 Sent to CCL by: Li qiang [cougarhead_2003##yahoo.com] --0-690508305-1291348194=:20547 Content-Type: text/plain; charset=iso-8859-1 Content-Transfer-Encoding: quoted-printable Hi CCL'ers: I have a somewhat strange TS locating problem wtih g03. My first run of loc= ating the TS was completed fine, with the output of the optimized TS coordi= nates: =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 Input orientation: =A0 = =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0=20 =A0---------------------------------------------------------------------= =20 =A0Center =A0 =A0 Atomic =A0 =A0 Atomic =A0 =A0 =A0 =A0 =A0 =A0 =A0Coordin= ates (Angstroms)=20 =A0Number =A0 =A0 Number =A0 =A0 =A0Type =A0 =A0 =A0 =A0 =A0 =A0 =A0X =A0 = =A0 =A0 =A0 =A0 Y =A0 =A0 =A0 =A0 =A0 Z=20 =A0---------------------------------------------------------------------= =20 =A0 =A0 1 =A0 =A0 =A0 =A0 =A09 =A0 =A0 =A0 =A0 =A0 =A0 0 =A0 =A0 =A0 -3.38= 6882 =A0 =A01.262162 =A0 -0.189094=20 =A0 =A0 2 =A0 =A0 =A0 =A0 =A01 =A0 =A0 =A0 =A0 =A0 =A0 0 =A0 =A0 =A0 -4.25= 2089 =A0 =A00.740968 =A0 =A00.231843=20 =A0 =A0 3 =A0 =A0 =A0 =A0 17 =A0 =A0 =A0 =A0 =A0 =A0 0 =A0 =A0 =A0 -5.4823= 26 =A0 -0.002357 =A0 =A00.832002=20 =A0---------------------------------------------------------------------= =20 because I saw the convergence in the optimization is: =A0 =A0 =A0 =A0=A0 Item =A0 =A0 =A0 =A0 =A0 =A0 =A0 Value =A0 =A0 Threshold= =A0Converged?=20 =A0Maximum Force =A0 =A0 =A0 =A0 =A0 =A00.000032 =A0 =A0 0.000450 =A0 =A0 = YES=20 =A0RMS =A0 =A0 Force =A0 =A0 =A0 =A0 =A0 =A00.000022 =A0 =A0 0.000300 =A0 = =A0 YES=20 =A0Maximum Displacement =A0 =A0 0.000697 =A0 =A0 0.001800 =A0 =A0 YES=20 =A0RMS =A0 =A0 Displacement =A0 =A0 0.000666 =A0 =A0 0.001200 =A0 =A0 YES= =20 =A0Predicted change in Energy=3D-1.988338D-08=20 =A0Optimization completed.=20 =A0 =A0 -- Stationary point found.=20 And the link1 freq calculation shows: Harmonic frequencies (cm**-1), IR intensities (KM/Mole), Raman scattering= =20 =A0activities (A**4/AMU), depolarization ratios for plane and unpolarized= =20 =A0incident light, reduced masses (AMU), force constants (mDyne/A),=20 =A0and normal coordinates:=20 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A01 =A0 =A0 =A0 =A0 =A0 =A0 =A0 = =A0 =A0 =A0 =A02 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A03=20 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0A =A0 =A0 =A0 =A0 =A0 =A0 =A0 = =A0 =A0 =A0 =A0A =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0A=20 =A0Frequencies -- -2672.6281 =A0 =A0 =A0 =A0 =A0 =A0 =A0 525.4568 =A0 =A0 = =A0 =A0 =A0 =A0 =A0 578.5686=20 =A0Red. masses -- =A0 =A0 1.0263 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A022.2631 = =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 1.0304=20 =A0Frc consts =A0-- =A0 =A0 4.3194 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 3.6217 = =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 0.2032=20 =A0IR Inten =A0 =A0-- =A07645.8759 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A016.4800 = =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A057.7877=20 =A0Atom AN =A0 =A0 =A0X =A0 =A0 =A0Y =A0 =A0 =A0Z =A0 =A0 =A0 =A0X =A0 =A0= =A0Y =A0 =A0 =A0Z =A0 =A0 =A0 =A0X =A0 =A0 =A0Y =A0 =A0 =A0Z=20 =A0 =A01 =A0 9 =A0 =A0-0.02 =A0-0.01 =A0 0.01 =A0 =A0 0.68 =A0 0.42 =A0-0.= 34 =A0 =A0-0.02 =A0 0.02 =A0-0.01=20 =A0 =A02 =A0 1 =A0 =A0 0.79 =A0 0.48 =A0-0.38 =A0 =A0 0.14 =A0-0.01 =A0 0.= 00 =A0 =A0 0.61 =A0-0.65 =A0 0.45=20 =A0 =A03 =A017 =A0 =A0-0.01 =A0-0.01 =A0 0.01 =A0 =A0-0.38 =A0-0.23 =A0 0.= 18 =A0 =A0-0.01 =A0 0.01 =A0-0.01=20 However, if I tried to start over to do a TS locating calculation using the= same theory/basis-level uhf/sto-3g opt(TS,calcall,noeigentest) nosymm as I= used in obtaining the stationary point and the freq calculation as above, = the job continued to run, seemingly to confirm the TS point found previousl= y was not the correct one. Could anyone please suggest what might go wrong = here? It is a very short run of g03; hope you can pleasea let me know what = you may get. Thanks a lot! =0A=0A=0A --0-690508305-1291348194=:20547 Content-Type: text/html; charset=iso-8859-1 Content-Transfer-Encoding: quoted-printable
Hi CCL'ers:

I have a somewhat strange = TS locating problem wtih g03. My first run of locating the TS was completed= fine, with the output of the optimized TS coordinates:

   = ;                     &nb= sp; Input orientation:               &nb= sp;          
 -------------------------= --------------------------------------------
 Center    = ; Atomic     Atomic             &nb= sp;Coordinates (Angstroms)
 Number     Number   &n= bsp;  Type              X   &n= bsp;       Y           Z
 = ;---------------------------------------------------------------------
    1          9       &= nbsp;     0       -3.386882    1.262162 =   -0.189094
    2          1 &= nbsp;           0       -4.252089 &= nbsp;  0.740968    0.231843
    3   &nbs= p;     17             0   &nbs= p;   -5.482326   -0.002357    0.832002
 -----= ----------------------------------------------------------------

be= cause I saw the convergence in the optimization is:
     =    Item               Value &= nbsp;   Threshold  Converged?
 Maximum Force   &nb= sp;        0.000032     0.000450    = ; YES
 RMS     Force            0.000022     0.000300     YES
 = Maximum Displacement     0.000697     0.001800   &= nbsp; YES
 RMS     Displacement     0.000666 =     0.001200     YES
 Predicted change in Ene= rgy=3D-1.988338D-08
 Optimization completed.
    -= - Stationary point found.

And the link1 freq calculation shows:
= Harmonic frequencies (cm**-1), IR intensities (KM/Mole), Raman scattering <= br>  activities (A**4/AMU), depolarization ratios for plane and unpola= rized
 incident light, reduced masses (AMU), force constants (mDy= ne/A),
 and normal coordinates:
        =              1       &nbs= p;              2       &= nbsp;              3
                     A &nb= sp;                    A =                      = ;A
 Frequencies -- -2672.6281           =     525.4568               578= .5686
 Red. masses --     1.0263       &= nbsp;        22.2631          =       1.0304
 Frc consts  --     4= .3194                 3.6217  =               0.2032
 IR Inte= n    --  7645.8759            =    16.4800               &nbs= p;57.7877
 Atom AN      X      Y      Z        X     &= nbsp;Y      Z        X     &nb= sp;Y      Z
   1   9    -0.02 =  -0.01   0.01     0.68   0.42  -0.34   &= nbsp;-0.02   0.02  -0.01
   2   1   &nbs= p; 0.79   0.48  -0.38     0.14  -0.01   0.00 =     0.61  -0.65   0.45
   3  17 &nb= sp;  -0.01  -0.01   0.01    -0.38  -0.23 &nbs= p; 0.18    -0.01   0.01  -0.01

However, if I tr= ied to start over to do a TS locating calculation using the same theory/bas= is-level uhf/sto-3g opt(TS,calcall,noeigentest) nosymm as I used in obtaini= ng the stationary point and the freq calculation as above, the job continue= d to run, seemingly to confirm the TS point found previously was not the correct one. Could anyone please suggest what might go wrong here? It = is a very short run of g03; hope you can pleasea let me know what you may g= et.

Thanks a lot!


=0A=0A --0-690508305-1291348194=:20547--