Friends, I am trying to calculate a TD= DFT spectra having 4 C-O bond in 2 plane. Both the planes are tilted by 153= degree. I got the experimental UV-VIS spectra up to 200nm (450 nm , 410 an= d 308 nm). But when I try to obtain the TDDFT spectra of the complex it onl= y shows spectral data up to 308 nm.=C2=A0 Several attempts with n states 60= also fails to reach beyond. Please help.

Does the planarity of both the ligand effects the UV-VIS transition ?=

=C2=A0The transition below probably due to n-Pi* transition.
<= /div>Regards,

Partha

--
Dr. Partha Sarathi Sengupta
Associate Professor
Vivekananda Mahavidya= laya, Burdwan

--047d7bea44c09bc4b1050114f312-- From owner-chemistry@ccl.net Thu Aug 21 07:18:01 2014 From: "Lars Goerigk lars.goerigk^-^unimelb.edu.au" To: CCL Subject: CCL: Inability to obtain theoretical UV-VIS spectra for Cu-O complex. Message-Id: <-50415-140821012526-27331-GCUcejhP4Bz0gSj/ofO6Tw]=[server.ccl.net> X-Original-From: Lars Goerigk Content-Language: en-US Content-Type: multipart/alternative; boundary="_000_01B46C31E2F94963BC53912295553E95unimelbeduau_" Date: Thu, 21 Aug 2014 05:23:19 +0000 MIME-Version: 1.0 Sent to CCL by: Lars Goerigk [lars.goerigk-#-unimelb.edu.au] --_000_01B46C31E2F94963BC53912295553E95unimelbeduau_ Content-Type: text/plain; charset="us-ascii" Content-Transfer-Encoding: quoted-printable Hi Partha, it depends on the code and the functional you are using. GGA functionals (and also hybrids up to a certain amount of Fock exchange) = can produce so called ghost states. Those are low-lying artificial states (= normally without any significant intensity) caused by the self-interaction = error. > From what you say it sounds a bit as if you are experiencing this problem. = One way to test this is to use a functional with a high portion of Fock exc= hange, such as BHLYP (BHandHLYP). It can lead to blue-shifted excitation en= ergies, but at least you can get a first idea about whether ghost states ar= e the reason for your problem. Alternatively you can use range-separated hy= brids or double-hybrids. The latter provide currently the most accurate exc= itation energies in a TD-DFT framework, but they are currently only availab= le for excited states in the ORCA program (see works by Grimme between 2007= and 2011 on this subject). Is your molecule symmetric? If yes, you could try to get hold of a code tha= t employs symmetry and that allows you to preselect how many roots per irre= ducible representation you would like to calculate. In this way, you avoid= spending computer time on the calculation of forbidden transitions that yo= u would not see in your experiment anyway. From my experience, the TD-DFT m= odule from TURBOMOLE (called escf) does a very good job at using symmetry i= n TD-DFT calculations. I hope this could help you a bit. With best wishes, Lars --- Dr. Lars Goerigk ARC DECRA Fellow School of Chemistry The University of Melbourne VIC 3010 Australia Research profile: http://www.chemistry.unimelb.edu.au/dr-lars-goerigk List of my publications: http://www.researcherid.com/rid/D-3717-2009 On 21 Aug 2014, at 5:53 am, Partha Sengupta anapspsmo=3D-=3Dgmail.com

> wrot= e: Friends, I am trying to calculate a TDDFT spectra having 4 C-O bond in 2 pl= ane. Both the planes are tilted by 153 degree. I got the experimental UV-VI= S spectra up to 200nm (450 nm , 410 and 308 nm). But when I try to obtain t= he TDDFT spectra of the complex it only shows spectral data up to 308 nm. = Several attempts with n states 60 also fails to reach beyond. Please help. Does the planarity of both the ligand effects the UV-VIS transition ? The transition below probably due to n-Pi* transition. Regards, Partha -- Dr. Partha Sarathi Sengupta Associate Professor Vivekananda Mahavidyalaya, Burdwan --_000_01B46C31E2F94963BC53912295553E95unimelbeduau_ Content-Type: text/html; charset="us-ascii" Content-ID: Content-Transfer-Encoding: quoted-printable Hi Partha,

it depends on the code and the functional you are using.

GGA functionals (and also hybrids up to a certain amount of Fock excha= nge) can produce so called ghost states. Those are low-lying artificial sta= tes (normally without any significant intensity) caused by the self-interac= tion error.

From what you say it sounds a bit as if you are experiencing this prob= lem. One way to test this is to use a functional with a high portion of Foc= k exchange, such as BHLYP (BHandHLYP). It can lead to blue-shifted excitati= on energies, but at least you can get a first idea about whether ghost states are the reason for your proble= m. Alternatively you can use range-separated hybrids or double-hybrids. The= latter provide currently the most accurate excitation energies in a TD-DFT= framework, but they are currently only available for excited states in the ORCA program (see works by Grimme= between 2007 and 2011 on this subject).

Is your molecule symmetric? If yes, you could try to get hold of a cod= e that employs symmetry and that allows you to preselect how many roots per= irreducible representation you would like to calculate. In this way,= you avoid spending computer time on the calculation of forbidden transitions that you would not see in your ex= periment anyway. From my experience, the TD-DFT module from TURBOMOLE (call= ed escf) does a very good job at using symmetry in TD-DFT calculations.

I hope this could help you a bit.

With best wishes,

Lars

---

Dr. Lars Goerigk

ARC DECRA Fellow

School of Chemistry

The University of Melbourne

VIC 3010

Australia

Research profile:

http://www.= chemistry.unimelb.edu.au/dr-lars-goerigk

List of my publications:

http://www.research= erid.com/rid/D-3717-2009

On 21 Aug 2014, at 5:53 am, Partha Sengupta anapspsmo=3D-=3Dgmail.com <owner-chemistry ~ ccl.net> wrote:

Friends, I am trying to calculate a TDDFT spectra having 4 C-O bond in= 2 plane. Both the planes are tilted by 153 degree. I got the experimental = UV-VIS spectra up to 200nm (450 nm , 410 and 308 nm). But when I try to obt= ain the TDDFT spectra of the complex it only shows spectral data up to 308 nm. Several attempts with n st= ates 60 also fails to reach beyond. Please help.

Does the planarity of both the ligand effects the UV-VIS transition ?

The transition below probably due to n-Pi* transition.

Regards,

Partha

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

--_000_01B46C31E2F94963BC53912295553E95unimelbeduau_-- From owner-chemistry@ccl.net Thu Aug 21 09:10:00 2014 From: "Brian Skinn bskinn .. alum.mit.edu" To: CCL Subject: CCL: Advances in computational capabilities Message-Id: <-50416-140821090845-14701-PVNF/iyjTmpGFtZT4jiivg],[server.ccl.net> X-Original-From: Brian Skinn Content-Type: multipart/alternative; boundary=047d7bb0498e51018a0501236bcb Date: Thu, 21 Aug 2014 09:08:19 -0400 MIME-Version: 1.0 Sent to CCL by: Brian Skinn [bskinn . alum.mit.edu] --047d7bb0498e51018a0501236bcb Content-Type: text/plain; charset=UTF-8 All, I recently acquired a copy of the Dover reprint of *Molecular Vibrations* (Wilson, Decius & Cross). As a testament to the progress in computational capability over the last several decades, I offer the following from page six: In principle, therefore, the forces between the atoms can be calculated *a priori* from the electronic wave equation, but in practice this is not mathematically feasible (except for H2), and it is necessary to postulate the forces in such a manner as to obtain agreement with experiment. Therefore, although it is theoretically possible to start with a model consisting of electrons and nuclei interacting coulombically and obeying the laws of quantum mechanics, in practice it is necessary to assume the nature of the equilibrium configuration and of the forces between the atoms .... Brian --047d7bb0498e51018a0501236bcb Content-Type: text/html; charset=UTF-8 Content-Transfer-Encoding: quoted-printable

All,

I recently acquired a copy of the = Dover reprint of Molecular Vibrations=C2=A0(Wilson, Decius & Cro= ss). =C2=A0As a testament to the progress in computational capability over = the last several decades, I offer the following from page six:

In principle, therefore, the forces between the atoms can be = calculated a priori=C2=A0from the electronic wave equation, but in p= ractice this is not mathematically feasible (except for H2), and it is nece= ssary to postulate the forces in such a manner as to obtain agreement with = experiment. =C2=A0Therefore, although it is theoretically possible to start= with a model consisting of electrons and nuclei interacting coulombically = and obeying the laws of quantum mechanics, in practice it is necessary to a= ssume the nature of the equilibrium configuration and of the forces between= the atoms ....

Brian

--047d7bb0498e51018a0501236bcb-- From owner-chemistry@ccl.net Thu Aug 21 09:59:01 2014 From: "John McKelvey jmmckel*gmail.com" To: CCL Subject: CCL: Inability to obtain theoretical UV-VIS spectra for Cu-O complex. Message-Id: <-50417-140821095544-3978-pF/qG072kawQuVJzM/sd+A()server.ccl.net> X-Original-From: John McKelvey Content-Type: multipart/alternative; boundary=001a113395920f89dc050124133f Date: Thu, 21 Aug 2014 09:55:33 -0400 MIME-Version: 1.0 Sent to CCL by: John McKelvey [jmmckel[a]gmail.com] --001a113395920f89dc050124133f Content-Type: text/plain; charset=UTF-8 Sorry, I forgot... You could/should(?) also use solvents in TDDFT , and also optimize GS geometry in same solvent. .. See papers by Denis Jacquemin (sp?). John On Thu, Aug 21, 2014 at 9:51 AM, John McKelvey wrote: > Following on to what Lars suggested... I would use B2PLYP or some other > double-hybrid and at least 6-311+G* or def2-TZVP basis sets, or larger. > > John McKelvey > > > On Thu, Aug 21, 2014 at 1:23 AM, Lars Goerigk lars.goerigk^-^ > unimelb.edu.au wrote: > >> Hi Partha, >> >> it depends on the code and the functional you are using. >> GGA functionals (and also hybrids up to a certain amount of Fock >> exchange) can produce so called ghost states. Those are low-lying >> artificial states (normally without any significant intensity) caused by >> the self-interaction error. >> From what you say it sounds a bit as if you are experiencing this >> problem. One way to test this is to use a functional with a high portion of >> Fock exchange, such as BHLYP (BHandHLYP). It can lead to blue-shifted >> excitation energies, but at least you can get a first idea about whether >> ghost states are the reason for your problem. Alternatively you can use >> range-separated hybrids or double-hybrids. The latter provide currently the >> most accurate excitation energies in a TD-DFT framework, but they are >> currently only available for excited states in the ORCA program (see works >> by Grimme between 2007 and 2011 on this subject). >> >> Is your molecule symmetric? If yes, you could try to get hold of a code >> that employs symmetry and that allows you to preselect how many roots per >> irreducible representation you would like to calculate. In this way, you >> avoid spending computer time on the calculation of forbidden transitions >> that you would not see in your experiment anyway. From my experience, the >> TD-DFT module from TURBOMOLE (called escf) does a very good job at using >> symmetry in TD-DFT calculations. >> >> I hope this could help you a bit. >> >> With best wishes, >> Lars >> >> >> --- >> Dr. Lars Goerigk >> ARC DECRA Fellow >> School of Chemistry >> The University of Melbourne >> VIC 3010 >> Australia >> >> Research profile: >> http://www.chemistry.unimelb.edu.au/dr-lars-goerigk >> List of my publications: >> http://www.researcherid.com/rid/D-3717-2009 >> >> >> >> >> On 21 Aug 2014, at 5:53 am, Partha Sengupta anapspsmo=-=gmail.com < >> owner-chemistry**ccl.net> wrote: >> >> Friends, I am trying to calculate a TDDFT spectra having 4 C-O bond >> in 2 plane. Both the planes are tilted by 153 degree. I got the >> experimental UV-VIS spectra up to 200nm (450 nm , 410 and 308 nm). But when >> I try to obtain the TDDFT spectra of the complex it only shows spectral >> data up to 308 nm. Several attempts with n states 60 also fails to reach >> beyond. Please help. >> Does the planarity of both the ligand effects the UV-VIS transition ? >> The transition below probably due to n-Pi* transition. >> Regards, >> Partha >> >> -- >> Dr. Partha Sarathi Sengupta >> Associate Professor >> Vivekananda Mahavidyalaya, Burdwan >> >> >> > > > -- > John McKelvey > 10819 Middleford Pl > Ft Wayne, IN 46818 > 260-489-2160 > jmmckel,,gmail.com > -- John McKelvey 10819 Middleford Pl Ft Wayne, IN 46818 260-489-2160 jmmckel,,gmail.com --001a113395920f89dc050124133f Content-Type: text/html; charset=UTF-8 Content-Transfer-Encoding: quoted-printable

Sorry, I forgot... You could/should(?) also use solve= nts in TDDFT , and also optimize GS geometry in same solvent. .. See papers= by Denis Jacquemin (sp?).

John

On Thu, Aug 21, 2014 at 9:51 AM, John Mc= Kelvey <jmmckel,,gmail.com> wrote:

Following on to what Lars suggested...=C2=A0 I would = use B2PLYP or some other double-hybrid and at least 6-311+G* or def2-TZVP b= asis sets, or larger.

John McKelvey

On Thu, Aug 21, 2014 at 1:23 AM, Lars Go= erigk lars.goerigk^-^un= imelb.edu.au <owner-chemistry,,ccl.net> wrote:

Hi Partha,

it depends on the code and the functional you are using.

GGA functionals (and also hybrids up to a certain amount of Fock excha= nge) can produce so called ghost states. Those are low-lying artificial sta= tes (normally without any significant intensity) caused by the self-interac= tion error.

From what you say it sounds a bit as if you are experiencing this prob= lem. One way to test this is to use a functional with a high portion of Foc= k exchange, such as BHLYP (BHandHLYP). It can lead to blue-shifted excitati= on energies, but at least you can get a first idea about whether ghost states are the reason for your proble= m. Alternatively you can use range-separated hybrids or double-hybrids. The= latter provide currently the most accurate excitation energies in a TD-DFT= framework, but they are currently only available for excited states in the ORCA program (see works by Grimme= between 2007 and 2011 on this subject).

Is your molecule symmetric? If yes, you could try to get hold of a cod= e that employs symmetry and that allows you to preselect how many roots per= irreducible representation =C2=A0you would like to calculate. In this way,= you avoid spending computer time on the calculation of forbidden transitions that you would not see in your ex= periment anyway. From my experience, the TD-DFT module from TURBOMOLE (call= ed escf) does a very good job at using symmetry in TD-DFT calculations.

I hope this could help you a bit.

With best wishes,

Lars

---

Dr. Lars Goerigk

ARC DECRA Fellow

School of Chemistry

The University of Melbourne

VIC 3010

Australia

Research profile:=C2=A0

http://www.chemistry.unimelb.edu.au/dr-lars-goerigk

List of my publications:

h= ttp://www.researcherid.com/rid/D-3717-2009

On 21 Aug 2014, at 5:53 am, Partha Sengupta anapspsmo=3D-=3Dgmail.com <owner-chemistry**ccl.net> = wrote:

Friends, I am trying to calculate a TDDFT spectra having 4 C-O bond in= 2 plane. Both the planes are tilted by 153 degree. I got the experimental = UV-VIS spectra up to 200nm (450 nm , 410 and 308 nm). But when I try to obt= ain the TDDFT spectra of the complex it only shows spectral data up to 308 nm.=C2=A0 Several attempts with n st= ates 60 also fails to reach beyond. Please help.

Does the planarity of both the ligand effects the UV-VIS transition ?

=C2=A0The transition below probably due to n-Pi* transition.

Regards,

Partha

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

--
John McKelvey
10819 Middleford PlFt Wayne, IN 46818
260-489-2160
jmmckel,,gmail.com

--
John McKelvey
10819 = Middleford Pl
Ft Wayne, IN 46818
260-489-2160
jmmckel,,gmail.com

--001a113395920f89dc050124133f-- From owner-chemistry@ccl.net Thu Aug 21 10:34:01 2014 From: "Jeff Rawson jeff.rawson(!)duke.edu" To: CCL Subject: CCL: Inability to obtain theoretical UV-VIS spectra for Cu-O complex. Message-Id: <-50418-140821100013-5877-fyMT4w71U7xq7a1V+GVFbA===server.ccl.net> X-Original-From: Jeff Rawson Content-Language: en-US Content-Type: multipart/alternative; boundary="_000_601CA31996A644148F0C777CBA49791Bdukeedu_" Date: Thu, 21 Aug 2014 13:59:58 +0000 MIME-Version: 1.0 Sent to CCL by: Jeff Rawson [jeff.rawson,duke.edu] --_000_601CA31996A644148F0C777CBA49791Bdukeedu_ Content-Type: text/plain; charset="Windows-1252" Content-Transfer-Encoding: quoted-printable Dear Lars, Can you suggest any references mentioning these =91ghost states=92? I ha= ve also seen, especially with large molecules, many low oscillator strength= states with B3LYP that are not predicted with range-corrected hybrids. In= my reading so far I haven=92t noted any mention of this particular manifes= tation of self-interaction error. It would be very helpful for me to under= stand it a little better, and to have some references to cite. Thanks, Jeff Rawson Michael Therien Group Duke University FFSC Rm 5324C 124 Science Drive Durham, NC 27708 On Aug 21, 2014, at 1:23 AM, Lars Goerigk lars.goerigk^-^unimelb.edu.au

> wrote: Hi Partha, it depends on the code and the functional you are using. GGA functionals (and also hybrids up to a certain amount of Fock exchange) = can produce so called ghost states. Those are low-lying artificial states (= normally without any significant intensity) caused by the self-interaction = error. > From what you say it sounds a bit as if you are experiencing this problem. = One way to test this is to use a functional with a high portion of Fock exc= hange, such as BHLYP (BHandHLYP). It can lead to blue-shifted excitation en= ergies, but at least you can get a first idea about whether ghost states ar= e the reason for your problem. Alternatively you can use range-separated hy= brids or double-hybrids. The latter provide currently the most accurate exc= itation energies in a TD-DFT framework, but they are currently only availab= le for excited states in the ORCA program (see works by Grimme between 2007= and 2011 on this subject). Is your molecule symmetric? If yes, you could try to get hold of a code tha= t employs symmetry and that allows you to preselect how many roots per irre= ducible representation you would like to calculate. In this way, you avoid= spending computer time on the calculation of forbidden transitions that yo= u would not see in your experiment anyway. From my experience, the TD-DFT m= odule from TURBOMOLE (called escf) does a very good job at using symmetry i= n TD-DFT calculations. I hope this could help you a bit. With best wishes, Lars --- Dr. Lars Goerigk ARC DECRA Fellow School of Chemistry The University of Melbourne VIC 3010 Australia Research profile: http://www.chemistry.unimelb.edu.au/dr-lars-goerigk List of my publications: http://www.researcherid.com/rid/D-3717-2009 On 21 Aug 2014, at 5:53 am, Partha Sengupta anapspsmo=3D-=3Dgmail.com

> w= rote: Friends, I am trying to calculate a TDDFT spectra having 4 C-O bond in 2 pl= ane. Both the planes are tilted by 153 degree. I got the experimental UV-VI= S spectra up to 200nm (450 nm , 410 and 308 nm). But when I try to obtain t= he TDDFT spectra of the complex it only shows spectral data up to 308 nm. = Several attempts with n states 60 also fails to reach beyond. Please help. Does the planarity of both the ligand effects the UV-VIS transition ? The transition below probably due to n-Pi* transition. Regards, Partha -- Dr. Partha Sarathi Sengupta Associate Professor Vivekananda Mahavidyalaya, Burdwan --_000_601CA31996A644148F0C777CBA49791Bdukeedu_ Content-Type: text/html; charset="Windows-1252" Content-ID: <7FFCC880D13A294480A6457C1ACE885A++namprd05.prod.outlook.com> Content-Transfer-Encoding: quoted-printable Dear Lars,

Can you suggest any references mentioning these =91ghost states= =92? I have also seen, especially with large molecules, many low osci= llator strength states with B3LYP that are not predicted with range-correct= ed hybrids. In my reading so far I haven=92t noted any mention of this particular manifestation of self-interaction error. &n= bsp;It would be very helpful for me to understand it a little better, and t= o have some references to cite.

Thanks,

Jeff Rawson

Michael Therien Group

Duke University

FFSC Rm 5324C

124 Science Drive

Durham, NC 27708

On Aug 21, 2014, at 1:23 AM, Lars Goerigk lars.goerigk^-^unimelb.edu.au <owner-chemistry++ccl.net> wrote:

Hi Partha,

it depends on the code and the functional you are using.

GGA functionals (and also hybrids up to a certain amount of Fock excha= nge) can produce so called ghost states. Those are low-lying artificial sta= tes (normally without any significant intensity) caused by the self-interac= tion error.

From what you say it sounds a bit as if you are experiencing this prob= lem. One way to test this is to use a functional with a high portion of Foc= k exchange, such as BHLYP (BHandHLYP). It can lead to blue-shifted excitati= on energies, but at least you can get a first idea about whether ghost states are the reason for your proble= m. Alternatively you can use range-separated hybrids or double-hybrids. The= latter provide currently the most accurate excitation energies in a TD-DFT= framework, but they are currently only available for excited states in the ORCA program (see works by Grimme= between 2007 and 2011 on this subject).

Is your molecule symmetric? If yes, you could try to get hold of a cod= e that employs symmetry and that allows you to preselect how many roots per= irreducible representation you would like to calculate. In this way,= you avoid spending computer time on the calculation of forbidden transitions that you would not see in your ex= periment anyway. From my experience, the TD-DFT module from TURBOMOLE (call= ed escf) does a very good job at using symmetry in TD-DFT calculations.

I hope this could help you a bit.

With best wishes,

Lars

---

Dr. Lars Goerigk

ARC DECRA Fellow

School of Chemistry

The University of Melbourne

VIC 3010

Australia

Research profile:

http://www.= chemistry.unimelb.edu.au/dr-lars-goerigk

List of my publications:

http://www.research= erid.com/rid/D-3717-2009

On 21 Aug 2014, at 5:53 am, Partha Sengupta anapspsmo=3D-=3Dgmail.com <owner-chemistry**ccl.net> wrote:

Friends, I am trying to calculate a TDDFT spectra having 4 C-O bond in= 2 plane. Both the planes are tilted by 153 degree. I got the experimental = UV-VIS spectra up to 200nm (450 nm , 410 and 308 nm). But when I try to obt= ain the TDDFT spectra of the complex it only shows spectral data up to 308 nm. Several attempts with n st= ates 60 also fails to reach beyond. Please help.

Does the planarity of both the ligand effects the UV-VIS transition ?

The transition below probably due to n-Pi* transition.

Regards,

Partha

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

--_000_601CA31996A644148F0C777CBA49791Bdukeedu_-- From owner-chemistry@ccl.net Thu Aug 21 12:29:00 2014 From: "John McKelvey jmmckel-$-gmail.com" To: CCL Subject: CCL: Inability to obtain theoretical UV-VIS spectra for Cu-O complex. Message-Id: <-50419-140821095156-2545-0VWsJTv4lzsK8bcFsMsvJA : server.ccl.net> X-Original-From: John McKelvey Content-Type: multipart/alternative; boundary=047d7bdc789e9d93e40501240435 Date: Thu, 21 Aug 2014 09:51:31 -0400 MIME-Version: 1.0 Sent to CCL by: John McKelvey [jmmckel.:.gmail.com] --047d7bdc789e9d93e40501240435 Content-Type: text/plain; charset=UTF-8 Following on to what Lars suggested... I would use B2PLYP or some other double-hybrid and at least 6-311+G* or def2-TZVP basis sets, or larger. John McKelvey On Thu, Aug 21, 2014 at 1:23 AM, Lars Goerigk lars.goerigk^-^unimelb.edu.au wrote: > Hi Partha, > > it depends on the code and the functional you are using. > GGA functionals (and also hybrids up to a certain amount of Fock exchange) > can produce so called ghost states. Those are low-lying artificial states > (normally without any significant intensity) caused by the self-interaction > error. > From what you say it sounds a bit as if you are experiencing this problem. > One way to test this is to use a functional with a high portion of Fock > exchange, such as BHLYP (BHandHLYP). It can lead to blue-shifted excitation > energies, but at least you can get a first idea about whether ghost states > are the reason for your problem. Alternatively you can use range-separated > hybrids or double-hybrids. The latter provide currently the most accurate > excitation energies in a TD-DFT framework, but they are currently only > available for excited states in the ORCA program (see works by Grimme > between 2007 and 2011 on this subject). > > Is your molecule symmetric? If yes, you could try to get hold of a code > that employs symmetry and that allows you to preselect how many roots per > irreducible representation you would like to calculate. In this way, you > avoid spending computer time on the calculation of forbidden transitions > that you would not see in your experiment anyway. From my experience, the > TD-DFT module from TURBOMOLE (called escf) does a very good job at using > symmetry in TD-DFT calculations. > > I hope this could help you a bit. > > With best wishes, > Lars > > > --- > Dr. Lars Goerigk > ARC DECRA Fellow > School of Chemistry > The University of Melbourne > VIC 3010 > Australia > > Research profile: > http://www.chemistry.unimelb.edu.au/dr-lars-goerigk > List of my publications: > http://www.researcherid.com/rid/D-3717-2009 > > > > > On 21 Aug 2014, at 5:53 am, Partha Sengupta anapspsmo=-=gmail.com < > owner-chemistry**ccl.net> wrote: > > Friends, I am trying to calculate a TDDFT spectra having 4 C-O bond in > 2 plane. Both the planes are tilted by 153 degree. I got the experimental > UV-VIS spectra up to 200nm (450 nm , 410 and 308 nm). But when I try to > obtain the TDDFT spectra of the complex it only shows spectral data up to > 308 nm. Several attempts with n states 60 also fails to reach beyond. > Please help. > Does the planarity of both the ligand effects the UV-VIS transition ? > The transition below probably due to n-Pi* transition. > Regards, > Partha > > -- > Dr. Partha Sarathi Sengupta > Associate Professor > Vivekananda Mahavidyalaya, Burdwan > > > -- John McKelvey 10819 Middleford Pl Ft Wayne, IN 46818 260-489-2160 jmmckel_-_gmail.com --047d7bdc789e9d93e40501240435 Content-Type: text/html; charset=UTF-8 Content-Transfer-Encoding: quoted-printable

Following on to what Lars suggested...=C2=A0 I would = use B2PLYP or some other double-hybrid and at least 6-311+G* or def2-TZVP b= asis sets, or larger.

John McKelvey

On Thu, Aug 21, 2014 at 1:23 AM, Lars Go= erigk lars.goerigk^-^unimelb.edu.au <= span dir=3D"ltr"><owner-chemistry_-_ccl.net> wrote:

Hi Partha,

it depends on the code and the functional you are using.

GGA functionals (and also hybrids up to a certain amount of Fock excha= nge) can produce so called ghost states. Those are low-lying artificial sta= tes (normally without any significant intensity) caused by the self-interac= tion error.

From what you say it sounds a bit as if you are experiencing this prob= lem. One way to test this is to use a functional with a high portion of Foc= k exchange, such as BHLYP (BHandHLYP). It can lead to blue-shifted excitati= on energies, but at least you can get a first idea about whether ghost states are the reason for your proble= m. Alternatively you can use range-separated hybrids or double-hybrids. The= latter provide currently the most accurate excitation energies in a TD-DFT= framework, but they are currently only available for excited states in the ORCA program (see works by Grimme= between 2007 and 2011 on this subject).

Is your molecule symmetric? If yes, you could try to get hold of a cod= e that employs symmetry and that allows you to preselect how many roots per= irreducible representation =C2=A0you would like to calculate. In this way,= you avoid spending computer time on the calculation of forbidden transitions that you would not see in your ex= periment anyway. From my experience, the TD-DFT module from TURBOMOLE (call= ed escf) does a very good job at using symmetry in TD-DFT calculations.

I hope this could help you a bit.

With best wishes,

Lars

---

Dr. Lars Goerigk

ARC DECRA Fellow

School of Chemistry

The University of Melbourne

VIC 3010

Australia

Research profile:=C2=A0

http://www.chemistry.unimelb.edu.au/dr-lars-goerigk

List of my publications:

h= ttp://www.researcherid.com/rid/D-3717-2009

On 21 Aug 2014, at 5:53 am, Partha Sengupta anapspsmo=3D-=3Dgmail.com <owner-chemistry**ccl.net> = wrote:

Friends, I am trying to calculate a TDDFT spectra having 4 C-O bond in= 2 plane. Both the planes are tilted by 153 degree. I got the experimental = UV-VIS spectra up to 200nm (450 nm , 410 and 308 nm). But when I try to obt= ain the TDDFT spectra of the complex it only shows spectral data up to 308 nm.=C2=A0 Several attempts with n st= ates 60 also fails to reach beyond. Please help.

Does the planarity of both the ligand effects the UV-VIS transition ?

=C2=A0The transition below probably due to n-Pi* transition.

Regards,

Partha

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

--
John McKelvey
10819 = Middleford Pl
Ft Wayne, IN 46818
260-489-2160
jmmckel_-_gmail.com

--047d7bdc789e9d93e40501240435-- From owner-chemistry@ccl.net Thu Aug 21 15:10:00 2014 From: "James Mao xjamesmao],[gmail.com" To: CCL Subject: CCL:G: what program gives the real symmetry? G09w or GaussView5.0.8 Message-Id: <-50420-140820174216-26725-zbZFQwxtfyy5pcouzVB/aA^_^server.ccl.net> X-Original-From: "James Mao" Content-Language: en-us Content-Type: multipart/alternative; boundary="----=_NextPart_000_000D_01CFBC9E.0FD5FAD0" Date: Wed, 20 Aug 2014 17:42:06 -0400 MIME-Version: 1.0 Sent to CCL by: "James Mao" [xjamesmao..gmail.com] This is a multi-part message in MIME format. ------=_NextPart_000_000D_01CFBC9E.0FD5FAD0 Content-Type: text/plain; charset="UTF-8" Content-Transfer-Encoding: quoted-printable I think symmetry is all about tolerance. One should have an idea about = the correct symmetry first, then set the tolerance to let=20 program to find it. In this sense GaussView is enough for me. =20 > From: owner-chemistry+xjamesmao=3D=3Dgmail.com##ccl.net = [mailto:owner-chemistry+xjamesmao=3D=3Dgmail.com##ccl.net] On Behalf Of = Brian Skinn bskinn|*|alum.mit.edu Sent: Wednesday, August 20, 2014 3:50 PM To: Mao, James X Subject: CCL:G: what program gives the real symmetry? G09w or = GaussView5.0.8 =20 I have found the VMD Symmetry Tool = to be = useful in evaluating symmetry, in particular since it allows user = selection of the tolerance for deviations from ideal symmetry, and = provides a fair bit of information about the symmetry elements found. =20 =20 On Wed, Aug 20, 2014 at 2:31 PM, Radu I radudownload[-]gmail.com = > = wrote: Sent to CCL by: "Radu I" [radudownload(a)gmail.com] Dear CCL users, For a Gaussian output file, one can find information about symmetry by = either reading the output file (A) or by using the GaussView package = (via Results>Summary (B) or via Edit>Point Group(C)). In my case, some = systems (same molecule but different functionals et al) posses a = symmetry according to G09w and a different one when viewing the results = using GaussView (sometimes even this package gives different symmetries: = using (B) I find C2v, while using (C) I get C4v, or another example (B) = gives C4v while (C) gives D4d). What of the above give the real symmetry = of my system? I thank you for your time and for your support! PS. The strings I'm looking for in the Gaussian output file are = "Framework group" and "\PG". In the case of the (C) method, I'm just = enabling the point group symmetry from the window opened by Edit>Point = Group; this gives the "Current point group". -=3D This is automatically added to each message by the mailing script = =3D-
or use:E-mail to administrators: CHEMISTRY-REQUEST^-^ccl.net = or usehttp://www.ccl.net/chemistry/sub_unsub.shtml

I think symmetry is all about tolerance. One should have an idea = about the correct symmetry first, then set the tolerance to let =

program to find it. In this sense GaussView is enough for = me.

From:= = owner-chemistry+xjamesmao=3D=3Dgmail.com##ccl.net = [mailto:owner-chemistry+xjamesmao=3D=3Dgmail.com##ccl.net] On Behalf = Of Brian Skinn bskinn|*|alum.mit.edu
Sent: Wednesday, = August 20, 2014 3:50 PM
To: Mao, James X =
Subject: CCL:G: what program gives the real symmetry? = G09w or GaussView5.0.8

I have = found the VMD = Symmetry Tool to be useful in evaluating symmetry, in particular = since it allows user selection of the tolerance for deviations from = ideal symmetry, and provides a fair bit of information about the = symmetry elements found.

On Wed, Aug 20, 2014 at 2:31 PM, Radu I = radudownload[-]gmail.com <owner-chemistry^-^ccl.net> = wrote:

Sent to CCL by: "Radu = I" [radudownload(a)gmail.com]

Dear CCL users,

For a = Gaussian output file, one can find information about symmetry by either = reading the output file (A) or by using the GaussView package (via = Results>Summary (B) or via Edit>Point Group(C)). In my case, some = systems (same molecule but different functionals et al) posses a = symmetry according to G09w and a different one when viewing the results = using GaussView (sometimes even this package gives different symmetries: = using (B) I find C2v, while using (C) I get C4v, or another example (B) = gives C4v while (C) gives D4d). What of the above give the real symmetry = of my system?

I thank you for your time and for your = support!

PS. The strings I'm looking for in the Gaussian = output file are "Framework group" and "\PG". In the = case of the (C) method, I'm just enabling the point group symmetry from = the window opened by Edit>Point Group; this gives the "Current = point group".

-=3D This is automatically added to = each message by the mailing script =3D-<br

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------=_NextPart_000_000D_01CFBC9E.0FD5FAD0-- From owner-chemistry@ccl.net Thu Aug 21 15:45:00 2014 From: "radu.download radu.download{=}gmail.com" To: CCL Subject: CCL:G: what program gives the real symmetry? G09w or GaussView5.0.8 Message-Id: <-50421-140821124650-30231-2g8a8rY52gpcT/ARnjvdQg[A]server.ccl.net> X-Original-From: "radu.download" Content-Type: multipart/alternative; boundary=001a11339b58257ee70501267631 Date: Thu, 21 Aug 2014 19:46:26 +0300 MIME-Version: 1.0 Sent to CCL by: "radu.download" [radu.download{}gmail.com] --001a11339b58257ee70501267631 Content-Type: text/plain; charset=UTF-8 Thank you for your help; unfortunately VMD's Symmetry Tool sees all my systems as C1 (for any tolerance). Returning to the initial question, which one of the two codes (Gaussian and GaussView) should I trust the most when I'm interested in the symmetry? Thank you! --001a11339b58257ee70501267631 Content-Type: text/html; charset=UTF-8 Content-Transfer-Encoding: quoted-printable

Thank you for your help; unfortun= ately VMD's Symmetry Tool sees all my systems as C1 (for any tolerance)= .

Returning to the initial question, which one of the two code= s (Gaussian and GaussView) should I trust the most when I'm interested = in the symmetry?

Thank you!

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G09w or GaussView5.0.8 Message-Id: <-50423-140821162741-26922-NqbpWkqXMbyMWorbU45NQA|-|server.ccl.net> X-Original-From: Geoffrey Hutchison Content-Transfer-Encoding: 8bit Content-Type: text/plain; charset=windows-1252 Date: Thu, 21 Aug 2014 16:27:33 -0400 Mime-Version: 1.0 (Apple Message framework v1283) Sent to CCL by: Geoffrey Hutchison [geoffh:pitt.edu] > I think symmetry is all about tolerance. One should have an idea about the correct symmetry first, then set the tolerance to let > program to find it. In this sense GaussView is enough for me. Indeed. I usually have students (both undergrad and grad) run some calculations on symmetric and nearly-symmetric molecules when I teach point-group symmetry. One issue is that if you optimize geometries in Cartesian coordinates, most programs will generate internal coordinates that are rarely symmetry-adapted. So it is frequently the case that an optimized geometry may end up in a subgroup (e.g., C2v or C4v rather than D4d) because of slight differences in bond lengths and angles. If it�s important to generate fully-symmetric geometries, you will often need to hand-edit a Z-matrix representation of the geometry to ensure bond lengths and angles are uniform. (For example, GAMESS-US requires only the symmetrically unique atoms for this. Other programs are similar.) Case in point, if you create C60 with GaussView using the library geometry in the GUI, the perceived symmetry is *not* Ih, and it does not optimize to Ih either. (I believe there are z-matrix input files on CCL.net for symmetry-adapted calculations of various fullerenes.) > From a teaching perspective, I consider that a feature, not a bug. :-) In the case of the original poster, the real symmetry of the calculation is given in your output file - that�s what Gaussian used when performing the calculations. The �real symmetry� is likely higher with careful optimizations. -Geoff --- Prof. Geoffrey Hutchison Department of Chemistry University of Pittsburgh tel: (412) 648-0492 email: geoffh{:}pitt.edu web: http://hutchison.chem.pitt.edu/ From owner-chemistry@ccl.net Thu Aug 21 17:30:00 2014 From: "Sebastian Kozuch seb.kozuch|-|gmail.com" To: CCL Subject: CCL:G: what program gives the real symmetry? G09w or GaussView5.0.8 Message-Id: <-50424-140821171335-2524-CaMlRvNdwrbFHSxoBse7EQ|server.ccl.net> X-Original-From: Sebastian Kozuch Content-Transfer-Encoding: 7bit Content-Type: text/plain; charset=windows-1252; format=flowed Date: Thu, 21 Aug 2014 16:13:22 -0500 MIME-Version: 1.0 Sent to CCL by: Sebastian Kozuch [seb.kozuch]_[gmail.com] Chemcraft is quite good for symmetrizing molecules. On 8/20/2014 1:31 PM, Radu I radudownload[-]gmail.com wrote: > Sent to CCL by: "Radu I" [radudownload(a)gmail.com] > > Dear CCL users, > > For a Gaussian output file, one can find information about symmetry by either reading the output file (A) or by using the GaussView package (via Results>Summary (B) or via Edit>Point Group(C)). In my case, some systems (same molecule but different functionals et al) posses a symmetry according to G09w and a different one when viewing the results using GaussView (sometimes even this package gives different symmetries: using (B) I find C2v, while using (C) I get C4v, or another example (B) gives C4v while (C) gives D4d). What of the above give the real symmetry of my system? > > I thank you for your time and for your support! > > > PS. The strings I'm looking for in the Gaussian output file are "Framework group" and "\PG". In the case of the (C) method, I'm just enabling the point group symmetry from the window opened by Edit>Point Group; this gives the "Current point group".> > -- xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx ..........Sebastian Kozuch........... xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx ......University of North Texas...... ..........Denton, Texas, USA......... ........ seb.kozuch]![gmail.com ....... http://yfaat.ch.huji.ac.il/kozuch.htm xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx From owner-chemistry@ccl.net Thu Aug 21 22:06:01 2014 From: "Lars Goerigk lars.goerigk]_[unimelb.edu.au" To: CCL Subject: CCL: Inability to obtain theoretical UV-VIS spectra for Cu-O complex. Message-Id: <-50425-140821215959-23418-17AlfectjY+mmvOqAKhmNw:-:server.ccl.net> X-Original-From: Lars Goerigk Content-Language: en-US Content-Type: multipart/alternative; boundary="_000_1AAE7D2CFAD94E4194C336C812D9C744unimelbeduau_" Date: Fri, 22 Aug 2014 01:58:23 +0000 MIME-Version: 1.0 Sent to CCL by: Lars Goerigk [lars.goerigk\a/unimelb.edu.au] --_000_1AAE7D2CFAD94E4194C336C812D9C744unimelbeduau_ Content-Type: text/plain; charset="Windows-1252" Content-Transfer-Encoding: quoted-printable Dear Jeff, those ghost-states are basically low-lying charge-transfer states and I gue= ss people started to report about them when they realised that TD-DFT with = common functionals has a problem with those states. It is outlined by Dreuw and Head-Gordon for zincbacteriochlorin-bacteriochl= orin, where standard functionals give a low-lying CT band, although it had = been established before that the lowest lying ones should be valence Q band= s: JACS 2004, 126, 4007. Below are some other papers that show some examples of ghost states and how= you can get rid of them. However, that is by far not a complete list, of c= ourse. - Neese, J. Biol. Inorg. Chem. 2006, 11, 702. - Several papers by the Grimme group: J. Phys. Chem. A 2009, 113, 767. PCCP 2009, 11, 4611. J. Chem. Phys. 2010, 132, 184103. - A very nice impressive example is the ECD spectrum of an alleno-acetyleni= c macrocycle. The system itself had originally been discussed by Diederich = and co-workers in Angew. Chem. Int. Ed. 2009, 48, 5545 , but we investigated it more in detail late= r in 2012. Unfortunately this is only published in a book chapter and I do = not know if you have access to it: Goerigk, Kruse, Grimme, =93Theoretical Electronic Circular Dichroism Spectr= oscopy of Large Organic and Supramolecular Systems=94, in =93Comprehensive = Chiroptical Spectroscopy=94, Vol. 1, Wiley, p.643, 2012. In that chapter we showed that TD-PBE (or any other TD-(meta-)GGA approach)= needs 60 excited states to cover the energy range of the system. This numb= er went down to 32 for PBE0 and B3LYP, to 19 for BHLYP and to only 12 for d= ouble-hybrids. Cheers, Lars --- Dr. Lars Goerigk ARC DECRA Fellow School of Chemistry The University of Melbourne VIC 3010 Australia Research profile: http://www.chemistry.unimelb.edu.au/dr-lars-goerigk List of my publications: http://www.researcherid.com/rid/D-3717-2009 On 21 Aug 2014, at 11:59 pm, Jeff Rawson jeff.rawson(!)duke.edu

> wrote: Dear Lars, Can you suggest any references mentioning these =91ghost states=92? I ha= ve also seen, especially with large molecules, many low oscillator strength= states with B3LYP that are not predicted with range-corrected hybrids. In= my reading so far I haven=92t noted any mention of this particular manifes= tation of self-interaction error. It would be very helpful for me to under= stand it a little better, and to have some references to cite. Thanks, Jeff Rawson Michael Therien Group Duke University FFSC Rm 5324C 124 Science Drive Durham, NC 27708 On Aug 21, 2014, at 1:23 AM, Lars Goerigk lars.goerigk^-^unimelb.edu.au

> w= rote: Friends, I am trying to calculate a TDDFT spectra having 4 C-O bond in 2 pl= ane. Both the planes are tilted by 153 degree. I got the experimental UV-VI= S spectra up to 200nm (450 nm , 410 and 308 nm). But when I try to obtain t= he TDDFT spectra of the complex it only shows spectral data up to 308 nm. = Several attempts with n states 60 also fails to reach beyond. Please help. Does the planarity of both the ligand effects the UV-VIS transition ? The transition below probably due to n-Pi* transition. Regards, Partha -- Dr. Partha Sarathi Sengupta Associate Professor Vivekananda Mahavidyalaya, Burdwan --_000_1AAE7D2CFAD94E4194C336C812D9C744unimelbeduau_ Content-Type: text/html; charset="Windows-1252" Content-ID: <8359ECE83B1FEC4A8C1F356F4ED5195F*exchange.unimelb.edu.au> Content-Transfer-Encoding: quoted-printable Dear Jeff,

those ghost-states are basically low-lying charge-transfer states and = I guess people started to report about them when they realised that TD-DFT = with common functionals has a problem with those states.

It is outlined by Dreuw and Head-Gordon for zincbacteriochlorin-bacter= iochlorin, where standard functionals give a low-lying CT band, although it= had been established before that the lowest lying ones should be valence Q= bands:

JACS 2004, 126, 4007.

Below are some other papers that show some examples of ghost states an= d how you can get rid of them. However, that is by far not a complete list,= of course.

- Neese, J. Biol. Inorg. Chem= . 2006, 11, 702.

- Several papers by the Grimme group:

J. Phys. Chem. A 2009, 113, 767.

PCCP 2009, 11, 4611.

J. Chem. Phys. 2010, 132, 184103.

- A very nice impressive example is the ECD spectrum of an alleno-acetyl= enic macrocycle. The system itself had originally been discussed by Di= ederich and co-workers in Angew.

Chem. Int. Ed. 2009, 48, 5545 , but we investigated it more in detail later in 2012= . Unfortunately this is only published in a book chapter and I do= not know if you have access to it:

Goerigk, Kruse, Grimme, =93Theoretical Electronic Circular Dichroism S= pectroscopy of Large Organic and Supramolecular Systems=94, in =93Comprehen= sive Chiroptical Spectroscopy=94, Vol. 1, Wiley, p.643, 2012.

In that chapter we showed that TD-PBE (or any other TD-(meta-)GGA appr= oach) needs 60 excited states to cover the energy range of the system. This= number went down to 32 for PBE0 and B3LYP, to 19 for BHLYP and to only 12 = for double-hybrids.

Cheers,

Lars <= /div>

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