From owner-chemistry@ccl.net Tue Jul 14 09:39:01 2015 From: "Jim Kress jimkress35/./gmail.com" To: CCL Subject: CCL: Rydberg orbital Message-Id: <-51529-150714084417-28623-IPUrcPX1zbe9RV7CQp3dhQ#server.ccl.net> X-Original-From: "Jim Kress" Content-Language: en-us Content-Type: multipart/alternative; boundary="----=_NextPart_000_0630_01D0BE11.3A5CB4E0" Date: Tue, 14 Jul 2015 08:43:58 -0400 MIME-Version: 1.0 Sent to CCL by: "Jim Kress" [jimkress35:+:gmail.com] This is a multipart message in MIME format. ------=_NextPart_000_0630_01D0BE11.3A5CB4E0 Content-Type: text/plain; charset="us-ascii" Content-Transfer-Encoding: 7bit The NBO methodology by Weinhold et al provides a clear definition, description and identification of Rydberg orbitals. I'd suggest you contact them at: http://nbo6.chem.wisc.edu/ Jim James Kress Ph.D., President The KressWorks Foundation C An IRS Approved 501 (c)(3) Charitable, Nonprofit Organization "Improving Lives One Atom At A Time" TM (248) 605-8770 Learn More and Donate At: http://www.kressworks.org Confidentiality Notice | This e-mail message, including any attachments, is for the sole use of the intended recipient(s) and may contain confidential or proprietary information. Any unauthorized review, use, disclosure or distribution is prohibited. If you are not the intended recipient, immediately contact the sender by reply e-mail and destroy all copies of the original message. > From: owner-chemistry+jimkress35==gmail.com:+:ccl.net [mailto:owner-chemistry+jimkress35==gmail.com:+:ccl.net] On Behalf Of Abrash, Samuel sabrash[*]richmond.edu Sent: Monday, July 13, 2015 7:52 PM To: Kress, Jim Subject: CCL: Rydberg orbital Rydberg orbitals were identified experimentally (in the 1920s I believe) because they had atomic-like spectral signatures in a molecular spectrum. Essentially they were interpreted as high lying excited states, far enough > from the nucleus that the rest of the electrons appear to be the core while the rydberg electron is interacting with the cationic core as a whole. (Almost as if the cationic core was a point charge.) This suggests a couple of diagnoses. First, the average distance from the nucleus should be significantly larger than for HOMO - 1. Second, especially for smaller, symmetric molecules, the rydberg orbitals can take on the appearance of unhybridized atomic orbitals, looking at an electron density diagram can help with the diagnosis. Best regards, Sam Sent from my iPhone On Jul 13, 2015, at 2:23 PM, Partha Sengupta anapspsmo++gmail.com > wrote: Friends, How can I identify the Rydberg type orbital in Gaussview ? What are the other criteria? Partha -- Dr. Partha Sarathi Sengupta Associate Professor Vivekananda Mahavidyalaya, Burdwan ------=_NextPart_000_0630_01D0BE11.3A5CB4E0 Content-Type: text/html; charset="us-ascii" Content-Transfer-Encoding: quoted-printable

The NBO methodology by Weinhold et al provides a clear definition, = description and identification of Rydberg = orbitals.

 

I’d suggest you contact them at:

 

http://nbo6.chem.wisc.edu/

 

Jim

 

James Kress Ph.D., President

The KressWorks Foundation ©

An IRS Approved 501 (c)(3) Charitable, Nonprofit = Organization

"Improving Lives One Atom At A Time" = TM

(248) 605-8770

 

Learn More and Donate At:

http://www.kressworks.org

 

Confidentiality Notice | This e-mail message, including any = attachments, is for the sole use of the intended recipient(s) and may = contain confidential or proprietary information. Any unauthorized = review, use, disclosure or distribution is prohibited. If you are not = the intended recipient, immediately contact the sender by reply e-mail = and destroy all copies of the original message.

 

From:<= /b> = owner-chemistry+jimkress35=3D=3Dgmail.com:+:ccl.net = [mailto:owner-chemistry+jimkress35=3D=3Dgmail.com:+:ccl.net] On Behalf = Of Abrash, Samuel sabrash[*]richmond.edu
Sent: Monday, = July 13, 2015 7:52 PM
To: Kress, Jim =
Subject: CCL: Rydberg = orbital

 

Rydberg = orbitals were identified experimentally (in the 1920s I believe) because = they had atomic-like spectral signatures in a molecular spectrum. =  Essentially they were interpreted as high lying excited states, = far enough from the nucleus that the rest of the electrons appear to be = the core while the rydberg electron is interacting with the cationic = core as a whole. (Almost as if the cationic core was a point = charge.)

 

This suggests a couple of diagnoses.  First, the = average distance from the nucleus should be significantly larger than = for HOMO - 1. Second, especially for smaller, symmetric molecules, the = rydberg orbitals can take on the appearance of unhybridized atomic = orbitals, looking at an electron density diagram can help with the = diagnosis.

 

Best regards,

Sam


Sent from my iPhone


On Jul 13, 2015, at = 2:23 PM, Partha Sengupta anapspsmo++gmail.com <owner-chemistry(0)ccl.net&g= t; wrote:

Friends, How can I identify the Rydberg type orbital = in Gaussview ?

What are the = other criteria?

Partha


-- =

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

=
------=_NextPart_000_0630_01D0BE11.3A5CB4E0-- From owner-chemistry@ccl.net Tue Jul 14 10:53:00 2015 From: "Puneet Gupta puneetg.iitk/./gmail.com" To: CCL Subject: CCL: M06L with D3 correction Message-Id: <-51530-150714105135-10345-v+EhYrnItyNRa4bBgdWFlg!^!server.ccl.net> X-Original-From: "Puneet Gupta" Date: Tue, 14 Jul 2015 10:51:34 -0400 Sent to CCL by: "Puneet Gupta" [puneetg.iitk : gmail.com] Dear All, Is it important to add D3 correction in M06L functional? Please guide me with your suggestion. The system I am working on contains hydrogen bonding interactions. Thanks! Kind regards, Puneet From owner-chemistry@ccl.net Tue Jul 14 13:55:00 2015 From: "Abrash, Samuel sabrash(a)richmond.edu" To: CCL Subject: CCL: M06L with D3 correction Message-Id: <-51531-150714124212-8313-w6mm1q0xBXWxwza8NbbySg * server.ccl.net> X-Original-From: "Abrash, Samuel" Content-Language: en-US Content-Transfer-Encoding: 8bit Content-Type: text/plain; charset="us-ascii" Date: Tue, 14 Jul 2015 16:42:05 +0000 MIME-Version: 1.0 Sent to CCL by: "Abrash, Samuel" [sabrash|richmond.edu] I was at the recent computational chemistry Gordon Conference, and Grimme spoke about the effect of D3 on various functionals. Since the M06 functional was parameterized with a molecule set for which dispersion was important, it does a good job of handling hydrogen bonding and other dispersion dependent interactions, even without D3. I believe D3 will still add a small improvement even though its use is not critical for M06. If I have this wrong, I believe Professor Grimme, who is also on this listserve, will chime in. I hope this is helpful. Sam Abrash Samuel A. Abrash Associate Professor, Department of Chemistry Coordinator, Environmental Studies Program University of Richmond sabrash++richmond.edu Cell: (804) 363-2597 www.richmond.edu/~sabrash "At the time God created the world and desired to reveal the depth of His being from out of the hidden, the light came from darkness and they were joined together. Because of this, out of darkness came the light, and out of the hidden came the revealed and out of the good came evil and out of mercy came severe judgement, and everything is intertwined with everything else... the good inclination and the evil inclination, the right and the left." The Zohar -----Original Message----- > From: owner-chemistry+sabrash==richmond.edu++ccl.net [mailto:owner-chemistry+sabrash==richmond.edu++ccl.net] On Behalf Of Puneet Gupta puneetg.iitk/./gmail.com Sent: Tuesday, July 14, 2015 10:52 AM To: Abrash, Samuel Subject: CCL: M06L with D3 correction Sent to CCL by: "Puneet Gupta" [puneetg.iitk : gmail.com] Dear All, Is it important to add D3 correction in M06L functional? Please guide me with your suggestion. The system I am working on contains hydrogen bonding interactions. Thanks! Kind regards, Puneethttp://www.ccl.net/cgi-bin/ccl/send_ccl_messagehttp://www.ccl.net/chemistry/sub_unsub.shtmlhttp://www.ccl.net/spammers.txt From owner-chemistry@ccl.net Tue Jul 14 14:30:01 2015 From: "Igors Mihailovs igors.mihailovs0]^[gmail.com" To: CCL Subject: CCL: M06L with D3 correction Message-Id: <-51532-150714142205-21651-+4gZDyeX03a93fLVFd5IAQ-,-server.ccl.net> X-Original-From: Igors Mihailovs Content-Type: multipart/alternative; boundary=001a1137ad2ee0447a051ad9e901 Date: Tue, 14 Jul 2015 21:21:38 +0300 MIME-Version: 1.0 Sent to CCL by: Igors Mihailovs [igors.mihailovs0*o*gmail.com] --001a1137ad2ee0447a051ad9e901 Content-Type: text/plain; charset=UTF-8 Dear Mr. Gupta, As M06-L is pure meta functional, being local by its nature, I think that for proper description of hydrogen bonding You will probably need dispersion correction. By the way, prof. Grimme himself suggests now to use D3BJ correction, if I correctly remember. With best wishes, Igors Mihailovs (engineer, Mg. chem.) Institute of Solid State Physics University of Latvia 2015-07-14 17:51 GMT+03:00 Puneet Gupta puneetg.iitk/./gmail.com < owner-chemistry~!~ccl.net>: > > Sent to CCL by: "Puneet Gupta" [puneetg.iitk : gmail.com] > Dear All, > > Is it important to add D3 correction in M06L functional? Please guide me > with your suggestion. The system I am working on contains hydrogen bonding > interactions. > > Thanks! > > Kind regards, > Puneet> > > --001a1137ad2ee0447a051ad9e901 Content-Type: text/html; charset=UTF-8 Content-Transfer-Encoding: quoted-printable
Dear Mr. Gupta,

As M06-L is pure meta f= unctional, being local by its nature, I think that for proper description o= f hydrogen bonding You will probably need dispersion correction. By the way= , prof. Grimme himself suggests now to use D3BJ correction, if I correctly = remember.

With best = wishes,
Igors Mihailovs (engineer, Mg. chem.)
I= nstitute of Solid State Physics
University of Latvia


2015-07-14 17:51 GMT+03:00 Puneet Gupta pune= etg.iitk/./gmail.com <= ;owner-chemist= ry~!~ccl.net>:

Sent to CCL by: "Puneet=C2=A0 Gupta" [puneetg.iitk : gmail.com]
Dear All,

Is it important to add D3 correction in M06L functional? Please guide me wi= th your suggestion. The system I am working on contains hydrogen bonding in= teractions.

Thanks!

Kind regards,
Puneet



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--001a1137ad2ee0447a051ad9e901-- From owner-chemistry@ccl.net Tue Jul 14 15:05:01 2015 From: "Mariusz Radon mariusz.radon===gmail.com" To: CCL Subject: CCL: M06L with D3 correction Message-Id: <-51533-150714142702-23367-9Mn8eBeOvKthsqLZDbviHw-.-server.ccl.net> X-Original-From: Mariusz Radon Content-Transfer-Encoding: 7bit Content-Type: text/plain; charset=windows-1252; format=flowed Date: Tue, 14 Jul 2015 20:26:29 +0200 MIME-Version: 1.0 Sent to CCL by: Mariusz Radon [mariusz.radon\a/gmail.com] On 07/14/2015 04:51 PM, Puneet Gupta puneetg.iitk/./gmail.com wrote: > Sent to CCL by: "Puneet Gupta" [puneetg.iitk : gmail.com] > Dear All, > > Is it important to add D3 correction in M06L functional? Please guide me with your suggestion. The system I am working on contains hydrogen bonding interactions. > > Thanks! > Dear Puneet: According to my recent experience with metal-nitrosyl species, the D3 correction matters much less for M06L than for other commonly used DFT methods (like B3LYP, TPSSh, BP86). You can find the details here: Inorg. Chem., 2015, 54, 5634-5645, DOI: 10.1021/ic503109a ; (see also Table S2, Supporting Information). However, I have no experience with M06L vs M06L-D3 for H-bonded systems. Anyway, since the correction is avaiable at virtually no extra computational cost, why not to include it (even if it might be not really important)? If you have already computed everything without the correction, you can make some tests on a few representative structures. These will give you an idea of how important might be the difference between the M06L and M06L-D3 energetics for your systems. Best regards, Mariusz -- Dr Mariusz Radon, Ph.D. Coordination Chemistry Group Faculty of Chemistry Jagiellonian University ul. Ingardena 3, 30-060 Krakow, Poland http://www2.chemia.uj.edu.pl/~mradon From owner-chemistry@ccl.net Tue Jul 14 16:10:01 2015 From: "Stefan Grimme grimme(a)thch.uni-bonn.de" To: CCL Subject: CCL: M06L with D3 correction Message-Id: <-51534-150714160638-25052-Puge4VMV6SWxmmtprx2yXg]|[server.ccl.net> X-Original-From: "Stefan Grimme" Date: Tue, 14 Jul 2015 16:06:37 -0400 Sent to CCL by: "Stefan Grimme" [grimme]|[thch.uni-bonn.de] >I was at the recent computational chemistry Gordon Conference, and Grimme spoke about the effect of D3 on >various functionals. Since the M06 functional was parameterized with a molecule set for which dispersion >was important, it does a good job of handling hydrogen bonding and other dispersion dependent interactions, >even without D3. I believe D3 will still add a small improvement even though its use is not critical for >M06. This is mostly correct. The M06... functionals totally miss the long to very long range dispersion part but include the short to medium range (overlap) part rather accurately. What is "long range" somewhat depends on size and dimensionality (1D vs. 3D) of the system and furthermore the property one is interested in. We recently investigated an 80 atom transition metal complex where the D3(0) correction to M06 improved the reaction (phosphane quenching) energy by 4-6 kcal/mol (5-10 % of the exp. value), see ChemistryOpen 2014, 3, 177-189. The corresponding effect for B3LYP is much larger, about 20-25 kcal/mol in the example to put this into perspective. The D3(BJ) version (which is the default for most other functionals) can not be used for the M06 class because of medium-range electron correlation double counting problems. Cheers! Stefan From owner-chemistry@ccl.net Tue Jul 14 19:15:00 2015 From: "Lars Goerigk lars.goerigk _ unimelb.edu.au" To: CCL Subject: CCL: M06L with D3 correction Message-Id: <-51535-150714191119-14659-om35ALVA4IZhmzWWEZWnJg..server.ccl.net> X-Original-From: Lars Goerigk Content-Language: en-US Content-Type: multipart/alternative; boundary="_000_E981B13824164CE0A6BBBAD6599FCE3Bunimelbeduau_" Date: Tue, 14 Jul 2015 23:10:12 +0000 MIME-Version: 1.0 Sent to CCL by: Lars Goerigk [lars.goerigk||unimelb.edu.au] --_000_E981B13824164CE0A6BBBAD6599FCE3Bunimelbeduau_ Content-Type: text/plain; charset="us-ascii" Content-Transfer-Encoding: quoted-printable Dear Mr Gupta, M06-L does not describe the asymptotic behaviour of the London dispersion e= nergy correctly and the consequences of this have been shown here: Chem. Phys. Chem. 2011, 12, 3421. Therefore, it can benefit from being combined with a dispersion correction.= However, due to the fact that it contains many parameters fitted to noncov= alent interaction energies, double-counting effects have been observed in t= he medium-range regime when it is combined with the Becke-Johnson damping function for DFT-D3. The= refore, it was only compatible with the zero-damping version, as described = in: PCCP 2011, 13, 6670. I hope this helped. Regards, 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 Follow me on Twitter: https://twitter.com/lgoer_compchem On 15 Jul 2015, at 12:51 am, Puneet Gupta puneetg.iitk/./gmail.com > wrote: Sent to CCL by: "Puneet Gupta" [puneetg.iitk : gmail.com= ] Dear All, Is it important to add D3 correction in M06L functional? Please guide me wi= th your suggestion. The system I am working on contains hydrogen bonding in= teractions. Thanks! Kind regards, Puneet -=3D This is automatically added to each message by the mailing script =3D-E-mail to subscribers: CHEMISTRY#,#ccl.net or use:E-mail to administrators: CHEMISTRY-REQUEST#,#ccl.net or usehttp://www.ccl.net/chemistry/sub_unsub.shtmlhttp://www.ccl.net/spammers.txt--_000_E981B13824164CE0A6BBBAD6599FCE3Bunimelbeduau_ Content-Type: text/html; charset="us-ascii" Content-ID: Content-Transfer-Encoding: quoted-printable Dear Mr Gupta,

M06-L does not describe the asymptotic behaviour of the London dispers= ion energy correctly and the consequences of this have been shown here:

Chem. Phys. Chem.  2011, 12, 3421.

Therefore, it can benefit from being combined with a dispersion correc= tion. However, due to the fact that it contains many parameters fitted to n= oncovalent interaction energies, double-counting effects have been observed= in the medium-range regime
when it is combined with the Becke-Johnson damping function for DFT-D3= . Therefore, it was only compatible with the zero-damping version, as descr= ibed in:

PCCP 2011, 13, 6670.


I hope this helped.

Regards,
Lars
---
Dr. Lars Goerigk
ARC DECRA Fellow
School of Chemistry
The University of Melbourne
VIC 3010
Australia

Research profile: 
List of my publications:

On 15 Jul 2015, at 12:51 am, Puneet Gupta puneetg.iitk/./gmail.com <owner-chemistry#,#ccl.net> wrote:


Sent to CCL by: "Puneet  Gupta" [puneetg.iitk : gmail.com]
Dear All,

Is it important to add D3 correction in M06L functional? Please guide me wi= th your suggestion. The system I am working on contains hydrogen bonding in= teractions.

Thanks!

Kind regards,
Puneet



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