From owner-chemistry@ccl.net Sun Jul 22 23:23:00 2018 From: "Lars Goerigk lars.goerigk:-:unimelb.edu.au" To: CCL Subject: CCL: PBE for inorganic chemistry Message-Id: <-53404-180722213549-30501-SAsFFDOgJIc8n708ZniT8Q:server.ccl.net> X-Original-From: Lars Goerigk Content-Language: en-US Content-Type: multipart/alternative; boundary="_000_DCFE5517D0CA437DB7E0695BB940DE90unimelbeduau_" Date: Mon, 23 Jul 2018 01:35:31 +0000 MIME-Version: 1.0 Sent to CCL by: Lars Goerigk [lars.goerigk%%unimelb.edu.au] --_000_DCFE5517D0CA437DB7E0695BB940DE90unimelbeduau_ Content-Type: text/plain; charset=WINDOWS-1252 Content-Transfer-Encoding: quoted-printable Hi Grigory, the big problem of having a zoo of DFT approximations is that it=92s hard t= o follow the literature for some and that many users therefore rely on popu= lar approaches. B3LYP and PBE are definitely two examples of the latter str= ategy. While the aforementioned =93Chemist=92s guide to DFT" is definitely a must-= read for people new to the field, the applications in the second half of th= at book are based on what people knew in the early 2000s. A lot has changed= since then and a lot of progress has been made. I therefore recommend these two papers from last year that can be considere= d as some of the largest DFT benchmark studies conducted for thermochemistr= y, kinetics and noncovalent interactions. I suggest to use them for guidanc= e. 1) Mol. Phys. 2017, 115, 2315. (Open Access) 2) Phys. Chem. Chem. Phys. 2017, 19, 32184 (Open Access) In a nutshell, there is no reason why PBE or B3LYP should be used in routin= e thermochemistry applications any more. If possible, double hybrids should= be used and if that is not feasible, any of the hybrids recommended in the= aforementioned papers. The story may be a bit different for transition met= al complexes, but overall the above recommendations could be used as a star= ting point in my opinion. Regarding double hybrids, most programs have effi= cient implementations of the resolution-of-the-identity MP2, and we run dou= ble hybrid applications routinely with large basis sets (usually QZ) and sy= stems with up to 50-80 atoms without any real problems. Some double hybrids= even scale N^4 is a Laplace transform algorithm is used. It is also important to use approaches that properly describe London disper= sion (even for geometries, reaction energies etc.), and I recommend DFT-D3(= BJ) or any of VV10-type van-der-Waals variants (sometimes called DFT-NL, so= metimes used with the suffix =93-V=94 as in Head-Gordon=92s B97M-V etc.). Note that despite popular belief, dispersion corrections should also be use= d for Minnesota functionals (both for equilibrium and non-equilibrium struc= tures): 3) J. Phys. Chem. Lett. 2015, 6, 3891. 4) J. Chem. Theory Comput. 2016, 12, 4303. 5) Ref. 2 from above Finally, do not fall into the B3LYP/6-31G* =93trap" as many DFT users still= do in joint experimental-computational collaborations: 6) J. Org. Chem. 2012, 77, 10824. I hope this helped. Cheers, Lars Dr Lars Goerigk | Lecturer Melbourne Centre for Theoretical & Computational Chemistry School of Chemistry | The University of Melbourne Victoria 3010 | Australia Website: http://goerigk.chemistry.unimelb.edu.au Follow me on Twitter: https://twitter.com/lgoer_compchem On 18 Jul 2018, at 3:51 am, Grigoriy Zhurko reg_zhurko.=-=.chemcraftprog.com<= http://chemcraftprog.com> > wrote: Sent to CCL by: Grigoriy Zhurko [reg_zhurko**chemcraftprog.com] I have heard that the PBE functional is often appropriate for inorganic che= mistry, while the B3LYP one is usually better for organic chemistry. Can yo= u help me find publications, in which the advantages of PBE for computing i= norganic molecules is described (for citing)? Grigoriy Zhurko https://chemcraftprog.com/ -=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 use Job: http://www.ccl.net/jobs --_000_DCFE5517D0CA437DB7E0695BB940DE90unimelbeduau_ Content-Type: text/html; charset=WINDOWS-1252 Content-ID: Content-Transfer-Encoding: quoted-printable Hi Grigory,

the big problem of having a zoo of DF= T approximations is that it=92s hard to follow the literature for some and = that many users therefore rely on popular approaches. B3LYP and PBE are def= initely two examples of the latter strategy.
While the aforementioned =93Chemist= =92s guide to DFT" is definitely a must-read for people new to the fie= ld, the applications in the second half of that book are based on what= people knew in the early 2000s. A lot has changed since then and a lot of progress has been made.

I therefore recommend these two paper= s from last year that can be considered as some of the largest DFT benchmar= k studies conducted for thermochemistry, kinetics and noncovalent interacti= ons. I suggest to use them for guidance.

1) Mol. Phys. 201= 7, 115, 2315. (Open Access)
2)
In a nutshell, there is no reason why= PBE or B3LYP should be used in routine thermochemistry applications any mo= re. If possible, double hybrids should be used and if that is not feasible,= any of the hybrids recommended in the aforementioned papers. The story may be a bit different for trans= ition metal complexes, but overall the above recommendations could be used = as a starting point in my opinion. Regarding double hybrids, most programs = have efficient implementations of the resolution-of-the-identity MP2, and we run double hybrid applications = ;routinely with large basis sets (usually QZ) and systems with up= to 50-80 atoms without any real problems. Some double hybrids even sc= ale N^4 is a Laplace transform algorithm is used.

It is also important to use approache= s that properly describe London dispersion (even for geometries, reaction e= nergies etc.), and I recommend DFT-D3(BJ) or any of VV10-type van-der-Waals= variants (sometimes called DFT-NL, sometimes used with the suffix =93-V=94 as in Head-Gordon=92s B97M-V etc.)= .
Note that despite popular belief, dis= persion corrections should also be used for Minnesota functionals (both for= equilibrium and non-equilibrium structures):

3) J. Phys. Chem. Lett.&n= bsp;2015, 6, 3891. 
4) J. Chem. Theory Comput. 2016, 12, 4303.
5) Ref. 2 from above

Finally, do not fall into the B3= LYP/6-31G* =93trap" as many DFT users still do in joint experimen= tal-computational collaborations:
6) J. Org. Chem. <= strong>2012, 77, 10824.

I hope this helped.

Cheers,
Lars

Dr Lars Goerigk | Lecturer 
Melbourne Centre for Theoretical & Computational Chemistry
School of Chemistry | The University of Melbourne
Victoria 3010 | Australia
Follow me on Twitter: https://twitter.com/lgoer_compchem



On 18 Jul 2018, at 3:51 am, Grigoriy Zhurko reg_zhurko.=-=.chemcraftprog.com <owner-chemistry=-=ccl.net> wrote:


Sent to CCL by: Grigoriy Zhurko [reg_zhurko**chemcraftprog.com]
I have heard that the PBE functional is often appropriate for inorganic che= mistry, while the B3LYP one is usually better for organic chemistry. Can yo= u help me find publications, in which the advantages of PBE for computing i= norganic molecules is described (for citing)?

Grigoriy Zhurko
https://chemcraftprog.com/



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