From owner-chemistry@ccl.net Tue Feb 11 04:19:00 2014 From: "Susi Lehtola susi.lehtola]![alumni.helsinki.fi" To: CCL Subject: CCL:G: How to consider charge on particular atom -lithium Message-Id: <-49654-140211041253-32435-0Px7K7iB0OaVOSHOzE3wOw{=}server.ccl.net> X-Original-From: Susi Lehtola Content-Transfer-Encoding: 8bit Content-Type: text/plain; charset=UTF-8 Date: Tue, 11 Feb 2014 11:12:44 +0200 MIME-Version: 1.0 Sent to CCL by: Susi Lehtola [susi.lehtola-.-alumni.helsinki.fi] On Mon, 10 Feb 2014 18:37:44 -0500 "Jim Kress ccl_nospam_._kressworks.com" wrote: > Sent to CCL by: "Jim Kress" [ccl_nospam,kressworks.com] > AIM and NBO charges would be the best choice. Mulliken and Lowdin are far too basis set dependent. NBO charges are explicitly dependent on the basis set, like Mulliken and Löwdin. AIM charges are not, but then again according to them e.g. H2O and HCN are ionic... Probably the best scheme is something like the recently proposed iterative Hirshfeld schemes, but I'm not aware of any program that implements these. Another possibility are electrostatic potential charges, which are available in e.g. Gaussian. -- --------------------------------------------------------------- Mr. Susi Lehtola, PhD Research Associate susi.lehtola\a/alumni.helsinki.fi Department of Applied Physics http://www.helsinki.fi/~jzlehtol Aalto University Finland --------------------------------------------------------------- Susi Lehtola, FT Tutkijatohtori susi.lehtola\a/alumni.helsinki.fi Fysiikan laitos http://www.helsinki.fi/~jzlehtol Aalto-yliopisto --------------------------------------------------------------- From owner-chemistry@ccl.net Tue Feb 11 08:08:00 2014 From: "Peeter Burk peeter.burk,ut.ee" To: CCL Subject: CCL:G: How to consider charge on particular atom -lithium Message-Id: <-49655-140211045652-27628-oL/7SbLb0LeeO3AiIAYYzg-.-server.ccl.net> X-Original-From: Peeter Burk Content-Transfer-Encoding: 8bit Content-Type: text/plain; charset=UTF-8; format=flowed Date: Tue, 11 Feb 2014 11:56:45 +0200 MIME-Version: 1.0 Sent to CCL by: Peeter Burk [peeter.burk[]ut.ee] Can you provide the reference to the "proof" that NBO charges are basis set dependent? My limited knowledge (based on e.g. Jensen's Introduction to comp. chem.) is that NBO charges are not sensitive to the size of basis set... By the way, my favourite paper on atomic charges is PRINCIPAL COMPONENTS OF IONICITY By: MEISTER, J; SCHWARZ, WHE JOURNAL OF PHYSICAL CHEMISTRY Volume: 98 Issue: 33 Pages: 8245-8252 which compares atomic charges calculated by 25 different schemes and states that "Only a single principal component of ionicity has been found...". By ionicity the authors mean atomic charges. Best regards Peeter On 02/11/2014 11:12 AM, Susi Lehtola susi.lehtola]![alumni.helsinki.fi wrote: > NBO charges are explicitly dependent on the basis set, like Mulliken > and Löwdin. > > AIM charges are not, but then again according to them e.g. H2O and HCN > are ionic... > > Probably the best scheme is something like the recently proposed > iterative Hirshfeld schemes, but I'm not aware of any program that > implements these. > > Another possibility are electrostatic potential charges, which are > available in e.g. Gaussian. > From owner-chemistry@ccl.net Tue Feb 11 08:55:01 2014 From: "Susi Lehtola susi.lehtola!=!alumni.helsinki.fi" To: CCL Subject: CCL: How to consider charge on particular atom -lithium Message-Id: <-49656-140211083728-23352-EfSnuIES4i4+8Elo/U4gZg|-|server.ccl.net> X-Original-From: Susi Lehtola Content-Transfer-Encoding: 8bit Content-Type: text/plain; charset=UTF-8 Date: Tue, 11 Feb 2014 15:37:16 +0200 MIME-Version: 1.0 Sent to CCL by: Susi Lehtola [susi.lehtola[*]alumni.helsinki.fi] On Tue, 11 Feb 2014 11:56:45 +0200 "Peeter Burk peeter.burk,ut.ee" wrote: > Sent to CCL by: Peeter Burk [peeter.burk[]ut.ee] > Can you provide the reference to the "proof" that NBO charges are basis > set dependent? My limited knowledge (based on e.g. Jensen's Introduction > to comp. chem.) is that NBO charges are not sensitive to the size of > basis set... You get NAOs/NBOs by identifying the atomic blocks of the density matrix, much like in Mulliken analysis. The procedure is explicitly dependent on the basis set, since only basis functions centered on an atom will contribute to its partial charge. In principle it's possible to span a complete basis set with functions on a single atom only, and for this case NBOs, Löwdin, Mulliken etc will assign all electrons in the system to that atom. Ergo, those methods do not even have a basis set limit, because the value you'll get depends on the way you approach basis set completeness. In contrast, methods that don't explicitly depend on the basis set (only implicitly through the representation of the electron density), such as Bader or ESP charge analysis, are a lot less sensitive to the basis set. -- --------------------------------------------------------------- Mr. Susi Lehtola, PhD Research Associate susi.lehtola ~ alumni.helsinki.fi Department of Applied Physics http://www.helsinki.fi/~jzlehtol Aalto University Finland --------------------------------------------------------------- Susi Lehtola, FT Tutkijatohtori susi.lehtola ~ alumni.helsinki.fi Fysiikan laitos http://www.helsinki.fi/~jzlehtol Aalto-yliopisto --------------------------------------------------------------- From owner-chemistry@ccl.net Tue Feb 11 09:48:00 2014 From: "Marcel Swart marcel.swart^-^icrea.cat" To: CCL Subject: CCL:G: How to consider charge on particular atom -lithium Message-Id: <-49657-140211092137-20821-oMGwKsedgn6NrU9gNhhnkA#%#server.ccl.net> X-Original-From: Marcel Swart Content-Type: multipart/alternative; boundary="Apple-Mail=_2FCD2AA0-BACB-4E25-930C-9194FAB0ACE2" Date: Tue, 11 Feb 2014 15:21:24 +0100 Mime-Version: 1.0 (Mac OS X Mail 7.1 \(1827\)) Sent to CCL by: Marcel Swart [marcel.swart-.-icrea.cat] --Apple-Mail=_2FCD2AA0-BACB-4E25-930C-9194FAB0ACE2 Content-Transfer-Encoding: quoted-printable Content-Type: text/plain; charset=iso-8859-1 E.g. see Figure 2 of: http://onlinelibrary.wiley.com/doi/10.1002/jcc.10351/abstract for the proof that Bader charges are basis set dependent. Marcel On 11 Feb 2014, at 10:56 , Peeter Burk peeter.burk,ut.ee = wrote: >=20 > Sent to CCL by: Peeter Burk [peeter.burk[]ut.ee] > Can you provide the reference to the "proof" that NBO charges are = basis set dependent? My limited knowledge (based on e.g. Jensen's = Introduction to comp. chem.) is that NBO charges are not sensitive to = the size of basis set... >=20 > By the way, my favourite paper on atomic charges is >=20 > PRINCIPAL COMPONENTS OF IONICITY > By: MEISTER, J; SCHWARZ, WHE > JOURNAL OF PHYSICAL CHEMISTRY Volume: 98 Issue: 33 Pages: = 8245-8252 >=20 > which compares atomic charges calculated by 25 different schemes and = states that "Only a single principal component of ionicity has been = found...". By ionicity the authors mean atomic charges. >=20 > Best regards > Peeter >=20 > On 02/11/2014 11:12 AM, Susi Lehtola susi.lehtola]![alumni.helsinki.fi = wrote: >> NBO charges are explicitly dependent on the basis set, like Mulliken >> and L=F6wdin. >>=20 >> AIM charges are not, but then again according to them e.g. H2O and = HCN >> are ionic... >>=20 >> Probably the best scheme is something like the recently proposed >> iterative Hirshfeld schemes, but I'm not aware of any program that >> implements these. >>=20 >> Another possibility are electrostatic potential charges, which are >> available in e.g. Gaussian. >>=20 >=20 >=20 >=20 > -=3D This is automatically added to each message by the mailing script = =3D- > To recover the email address of the author of the message, please = change>=20>=20>=20=>=20>=20Conferences: = http://server.ccl.net/chemistry/announcements/conferences/ >=20>=20>=20>=20 >=20 =3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D= =3D=3D=3D=3D=3D=3D=3D=3D=3D=3D Prof. Dr. Marcel Swart ICREA Research Professor at Institut de Qu=EDmica Computacional i Cat=E0lisi Universitat de Girona Facultat de Ci=E8ncies Campus Montilivi 17071 Girona Catalunya (Spain) tel +34-972-418861 fax +34-972-418356 e-mail marcel.swart|a|icrea.cat marcel.swart|a|udg.edu web http://www.marcelswart.eu vCard addressbook://www.marcelswart.eu/MSwart.vcf =3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D= =3D=3D=3D=3D=3D=3D=3D=3D=3D=3D --Apple-Mail=_2FCD2AA0-BACB-4E25-930C-9194FAB0ACE2 Content-Transfer-Encoding: quoted-printable Content-Type: text/html; charset=iso-8859-1
E.g. see Figure 2 of:
htt= p://onlinelibrary.wiley.com/doi/10.1002/jcc.10351/abstract
for = the proof that Bader charges are basis set = dependent.

Marcel

On 11 = Feb 2014, at 10:56 , Peeter Burk peeter.burk,ut.ee = <owner-chemistry|a|ccl.net> wrote:


Sent = to CCL by: Peeter Burk [peeter.burk[]ut.ee]
Can you provide the = reference to the "proof" that NBO charges are basis set dependent? My = limited knowledge (based on e.g. Jensen's Introduction to comp. chem.) = is that NBO charges are not sensitive to the size of basis = set...

By the way, my favourite paper on atomic charges = is

PRINCIPAL COMPONENTS OF IONICITY
By: MEISTER, J; SCHWARZ, = WHE
JOURNAL OF PHYSICAL CHEMISTRY  Volume: 98   Issue: = 33   Pages: 8245-8252

which compares atomic charges = calculated by 25 different schemes and states that "Only a single = principal component of ionicity has been found...". By ionicity the = authors mean atomic charges.

Best regards
Peeter

On = 02/11/2014 11:12 AM, Susi Lehtola susi.lehtola]![alumni.helsinki.fi = wrote:
NBO charges are explicitly dependent = on the basis set, like Mulliken
and L=F6wdin.

AIM charges are = not, but then again according to them e.g. H2O and HCN
are = ionic...

Probably the best scheme is something like the recently = proposed
iterative Hirshfeld schemes, but I'm not aware of any = program that
implements these.

Another possibility are = electrostatic potential charges, which are
available in e.g. = Gaussian.




-=3D This is automatically = added to each message by the mailing script =3D-
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Prof= . Dr. Marcel Swart

ICREA Research Professor at
Institut de = Qu=EDmica Computacional i Cat=E0lisi
Universitat de = Girona

Facultat de Ci=E8ncies
Campus Montilivi
17071 Girona
Catalunya = (Spain)

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marcel.swart|a|udg.edu
web
http://www.marce= lswart.eu

To: CCL Subject: CCL:G: How to consider charge on particular atom -lithium Message-Id: <-49658-140211102215-4941-eHfa3kw6oqYy1fFTFAObag-x-server.ccl.net> X-Original-From: "Jim Kress" Content-Language: en-us Content-Transfer-Encoding: 8bit Content-Type: text/plain; charset="utf-8" Date: Tue, 11 Feb 2014 10:22:13 -0500 MIME-Version: 1.0 Sent to CCL by: "Jim Kress" [ccl_nospam#,#kressworks.com] Misquoting people is a bad trait in a scientific discussion. My statement: "AIM and NBO charges would be the best choice. Mulliken and Lowdin are far too basis set dependent." does not say, at least in the English spoken in America, that AIM and NBO charges are basis set independent. What is does say, is that they are better choices than Milliken and Lowdin. If you bother to read Cramer's "Essentials of Computational Chemistry" and the rest of the applicable literature, you will find that the statement I made is generally accepted as being correct. Jim Kress -----Original Message----- > From: owner-chemistry+ccl_nospam==kressworks.com- -ccl.net [mailto:owner-chemistry+ccl_nospam==kressworks.com- -ccl.net] On Behalf Of Susi Lehtola susi.lehtola]![alumni.helsinki.fi Sent: Tuesday, February 11, 2014 4:13 AM To: Kress, Jim Subject: CCL:G: How to consider charge on particular atom -lithium Sent to CCL by: Susi Lehtola [susi.lehtola-.-alumni.helsinki.fi] On Mon, 10 Feb 2014 18:37:44 -0500 "Jim Kress ccl_nospam_._kressworks.com" wrote: > Sent to CCL by: "Jim Kress" [ccl_nospam,kressworks.com] AIM and NBO > charges would be the best choice. Mulliken and Lowdin are far too basis set dependent. NBO charges are explicitly dependent on the basis set, like Mulliken and Löwdin. AIM charges are not, but then again according to them e.g. H2O and HCN are ionic... Probably the best scheme is something like the recently proposed iterative Hirshfeld schemes, but I'm not aware of any program that implements these. Another possibility are electrostatic potential charges, which are available in e.g. Gaussian. -- --------------------------------------------------------------- Mr. Susi Lehtola, PhD Research Associate susi.lehtola%a%alumni.helsinki.fi Department of Applied Physics http://www.helsinki.fi/~jzlehtol Aalto University Finland --------------------------------------------------------------- Susi Lehtola, FT Tutkijatohtori susi.lehtola%a%alumni.helsinki.fi Fysiikan laitos http://www.helsinki.fi/~jzlehtol Aalto-yliopisto ---------------------------------------------------------------http://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 Feb 11 10:58:00 2014 From: "Evert Jan Baerends e.j.baerends]=[vu.nl" To: CCL Subject: CCL: atomic charges Message-Id: <-49659-140211103243-12811-9zUnCXGfQDLavvFBqBypyA+/-server.ccl.net> X-Original-From: "Evert Jan Baerends" Date: Tue, 11 Feb 2014 10:32:42 -0500 Sent to CCL by: "Evert Jan Baerends" [e.j.baerends,,vu.nl] An extensive discussion of various schemes to calculate atomic charges can be found in C. Fonseca Guerra et al. , J. Comput. Chem. 25 (2003) 189-210 " Voronoi Deformation Density (VDD) charges: assessment of the Mulliken, Bader, Hirshfeld, Weinhold and VDD methods for charge analysis" This paper concludes that Hirshfeld and VDD charges (which are numerically very close) are the least basis set dependent and the most realistic ("chemically meaningful"). This is because they are based on the spatial electron density rho(r) and do not use the basis set used to calculate rho(r) for the calculation or definition of the charges. The ADF code provides all these charges, including Hirshfeld and VDD. From owner-chemistry@ccl.net Tue Feb 11 11:32:01 2014 From: "Dr. Vitaly Chaban vvchaban[#]gmail.com" To: CCL Subject: CCL:G: Converges using HF and hybrid DFT, but fails to converge using pure DFT Message-Id: <-49660-140211110117-15406-I0wan5JuQk9EydnR84yNPA^server.ccl.net> X-Original-From: "Dr. Vitaly Chaban" Content-Type: text/plain; charset=ISO-8859-1 Date: Tue, 11 Feb 2014 17:00:25 +0100 MIME-Version: 1.0 Sent to CCL by: "Dr. Vitaly Chaban" [vvchaban__gmail.com] Dear All - The wavefunction for the system consisting of 2nd and 3rd row elements converges (at least to 10^(-7) Ha) using HF and hybrid DFT with modest basis set, but it does not converge appropriately (converges only to 10^(-4) Ha) using pure DFT functionals. The geometry is close to minimum, the cheap solutions, such as VShift, NoVarAcc, Guess=Read do not work. Which keyword(s) in Gaussian'09 would you suggest to enhance the SCF convergence in this case? Dr. Vitaly V. Chaban From owner-chemistry@ccl.net Tue Feb 11 12:52:00 2014 From: "Susi Lehtola susi.lehtola%alumni.helsinki.fi" To: CCL Subject: CCL: How to consider charge on particular atom -lithium Message-Id: <-49661-140211124741-14961-AH778h4Z10FjPYlXBZQR2A=-=server.ccl.net> X-Original-From: Susi Lehtola Content-Transfer-Encoding: 8bit Content-Type: text/plain; charset=UTF-8 Date: Tue, 11 Feb 2014 19:47:30 +0200 MIME-Version: 1.0 Sent to CCL by: Susi Lehtola [susi.lehtola---alumni.helsinki.fi] On Tue, 11 Feb 2014 10:22:13 -0500 "Jim Kress ccl_nospam+/-kressworks.com" wrote: > Sent to CCL by: "Jim Kress" [ccl_nospam#,#kressworks.com] > Misquoting people is a bad trait in a scientific discussion. > > My statement: > > "AIM and NBO charges would be the best choice. Mulliken and Lowdin are far too basis set dependent." > > does not say, at least in the English spoken in America, that AIM and NBO charges are basis set independent. Surely not. But, my point was that NBOs are still *explicitly dependent* on the basis set, and likely have similar basis set behavior as Mulliken and Löwdin. In contrast, e.g. AIM, Hirshfeld and ESP charges are only implicitly dependent on the basis set, and thus a) they have a basis set limit and b) they also converge faster. These are the methods one should really look at to get well defined partial charges. -- --------------------------------------------------------------- Mr. Susi Lehtola, PhD Research Associate susi.lehtola|alumni.helsinki.fi Department of Applied Physics http://www.helsinki.fi/~jzlehtol Aalto University Finland --------------------------------------------------------------- Susi Lehtola, FT Tutkijatohtori susi.lehtola|alumni.helsinki.fi Fysiikan laitos http://www.helsinki.fi/~jzlehtol Aalto-yliopisto --------------------------------------------------------------- From owner-chemistry@ccl.net Tue Feb 11 13:26:00 2014 From: "Tian Lu sobereva-x-sina.com" To: CCL Subject: CCL:G: How to consider charge on particular atom -lithium Message-Id: <-49662-140211100903-29763-1UidyRA/sBPQoQmJHSzGeA[-]server.ccl.net> X-Original-From: "Tian Lu" Date: Tue, 11 Feb 2014 10:09:02 -0500 Sent to CCL by: "Tian Lu" [sobereva/./sina.com] Hi, AFAIK, there is only one public program can realize Hirshfeld-I, namely HiPart (http://molmod.ugent.be/software/). Another modified Hirshfeld-based method alternative to Hirshfeld-I is atomic dipole moment corrected Hirshfeld (ADCH) population method, which is the one I highly recommend, see J. Theor. Comp. Chem., 2012, 11: 163-183. ADCH charges have much better reproducibility for electrostatic potential than Hirshfeld charges, and the molecular dipole moment can be even exactly reproduced. ADCH has been implemented in Multiwfn program (http://Multiwfn.codeplex.com, see Section 4.7.2 of its manual for example). NPA charges (also known as NBO charges) are also nice choice. In fact they are not explicitly dependent on but only indirectly dependent on the basis-set, because the original basis functions will be first transformed to natural atomic orbitals before performing natural population analysis, this step conspicuously reduces the sensitivity of NPA charges to basis-set. According to my experiences, the relative sensitivity to basis-set is Mulliken>=Lowdin>>NPAAIMcharges by fitting ESP (MK,CHELPG,etc.) >= HirshfeldADCH. Personally I don't recommend using AIM charges, since calculating AIM charges is usually time-consuming, and their reproducibility for observable quantities are quite poor. A comprehensive comparison of atomic charges can be found in Acta Phys.-Chim. Sinica, 2011, 28: 1-18 (http://www.whxb.pku.edu.cn/EN/abstract/abstract27818.shtml) Tian Lu ----- Original Message ----- > From: "Susi Lehtola susi.lehtola]![alumni.helsinki.fi" To: "Lu, Tian " Subject: CCL:G: How to consider charge on particular atom -lithium Date: 2014-02-11 17:12 Sent to CCL by: Susi Lehtola [susi.lehtola-.-alumni.helsinki.fi] On Mon, 10 Feb 2014 18:37:44 -0500 "Jim Kress ccl_nospam_._kressworks.com" wrote: > Sent to CCL by: "Jim Kress" [ccl_nospam,kressworks.com] > AIM and NBO charges would be the best choice. Mulliken and Lowdin are far too basis set dependent. NBO charges are explicitly dependent on the basis set, like Mulliken and Lwdin. AIM charges are not, but then again according to them e.g. H2O and HCN are ionic... Probably the best scheme is something like the recently proposed iterative Hirshfeld schemes, but I'm not aware of any program that implements these. Another possibility are electrostatic potential charges, which are available in e.g. Gaussian. -- --------------------------------------------------------------- Mr. Susi Lehtola, PhD Research Associate susi.lehtola%a%alumni.helsinki.fi Department of Applied Physics http://www.helsinki.fi/~jzlehtol Aalto University Finland --------------------------------------------------------------- Susi Lehtola, FT Tutkijatohtori susi.lehtola%a%alumni.helsinki.fi Fysiikan laitos http://www.helsinki.fi/~jzlehtol Aalto-yliopisto From owner-chemistry@ccl.net Tue Feb 11 14:01:00 2014 From: "Jason D Acchioli jdacchio,+,gmail.com" To: CCL Subject: CCL:G: How to consider charge on particular atom -lithium Message-Id: <-49663-140211101704-2189-PHHR55a247ZXBgAIEzyGIA]*[server.ccl.net> X-Original-From: "Jason D'Acchioli" Content-Type: multipart/alternative; boundary="Apple-Mail=_E25EC531-7A2B-4162-8AA1-9101D8F4CF43" Date: Tue, 11 Feb 2014 09:16:47 -0600 Mime-Version: 1.0 (Mac OS X Mail 7.1 \(1827\)) Sent to CCL by: "Jason D'Acchioli" [jdacchio%%gmail.com] --Apple-Mail=_E25EC531-7A2B-4162-8AA1-9101D8F4CF43 Content-Transfer-Encoding: quoted-printable Content-Type: text/plain; charset=utf-8 Hi all, You can find the following description at Landis and = Weinhold=E2=80=99s NBO site, http://nbo6.chem.wisc.edu/webnbo_css.htm. = You can also find more rigorous descriptions in their 2005 book = =E2=80=9CValency and Bonding=E2=80=9D. In principle, NBOs are basis set = independent; in practice, there is variance in charge.=20 Not to tout our own horn, but we recently published a paper = examining natural charges in a series of allyl systems. The supplemental = info (available here, = http://link.springer.com/article/10.1007%2Fs10904-013-9972-0) shows the = slight variance in basis set, but not much.=20 Jason Note that the wavefunction =CE=A8 is commonly described with the help of = chosen "basis orbitals" {=CF=87k} (such as those of a 6-311++G** basis = set, as employed in numerical work described below). However, for given = =CE=A8 the solutions of Eq. (1) are in principleindependent of the = chosen basis orbitals, whether of Slater, Gaussian, or plane wave type. = Indeed, the NOs and associated orbital-based concepts remain rigorously = defined by Eq. (1) even if =CE=A8 is specified only in interparticle = (Hylleraas or James-Coolidge typerij) coordinates, without reference to = any orbital basis set whatsoever. While it is often numerically = convenient to employ basis orbitals (orthogonal or non-orthogonal) to = solve eigenvalue problems such as Eq. (1), it is important to realize = that the eigenorbitals =CE=98k are in principle independent of the = particular basis orbitals chosen. Natural orbitals =CE=98k are intrinsic = and unique to =CE=A8, whereas basis orbitals =CF=87k are non-unique = "fitting" functions, chosen merely for numerical convenience. On Feb 11, 2014, at 3:56 AM, Peeter Burk peeter.burk,ut.ee = wrote: >=20 > Sent to CCL by: Peeter Burk [peeter.burk[]ut.ee] > Can you provide the reference to the "proof" that NBO charges are = basis set dependent? My limited knowledge (based on e.g. Jensen's = Introduction to comp. chem.) is that NBO charges are not sensitive to = the size of basis set... >=20 > By the way, my favourite paper on atomic charges is >=20 > PRINCIPAL COMPONENTS OF IONICITY > By: MEISTER, J; SCHWARZ, WHE > JOURNAL OF PHYSICAL CHEMISTRY Volume: 98 Issue: 33 Pages: = 8245-8252 >=20 > which compares atomic charges calculated by 25 different schemes and = states that "Only a single principal component of ionicity has been = found...". By ionicity the authors mean atomic charges. >=20 > Best regards > Peeter >=20 > On 02/11/2014 11:12 AM, Susi Lehtola susi.lehtola]![alumni.helsinki.fi = wrote: >> NBO charges are explicitly dependent on the basis set, like Mulliken >> and L=C3=B6wdin. >>=20 >> AIM charges are not, but then again according to them e.g. H2O and = HCN >> are ionic... >>=20 >> Probably the best scheme is something like the recently proposed >> iterative Hirshfeld schemes, but I'm not aware of any program that >> implements these. >>=20 >> Another possibility are electrostatic potential charges, which are >> available in e.g. Gaussian. >>=20 >=20 >=20 >=20 > -=3D This is automatically added to each message by the mailing script = =3D- > To recover the email address of the author of the message, please = change>=20>=20>=20=>=20>=20Conferences: = http://server.ccl.net/chemistry/announcements/conferences/ >=20>=20>=20>=20 >=20 --Apple-Mail=_E25EC531-7A2B-4162-8AA1-9101D8F4CF43 Content-Transfer-Encoding: quoted-printable Content-Type: text/html; charset=utf-8
Hi all,

You can = find the following description at Landis and Weinhold=E2=80=99s NBO = site, http://nbo6.chem.wisc.ed= u/webnbo_css.htm. You can also find more rigorous descriptions in = their 2005 book =E2=80=9CValency and Bonding=E2=80=9D. In principle, = NBOs are basis set independent; in practice, there is variance in = charge. 

Not to tout our own horn, but we = recently published a paper examining natural charges in a series of = allyl systems. The supplemental info (available here, http= ://link.springer.com/article/10.1007%2Fs10904-013-9972-0) shows the = slight variance in basis set, but not = much. 

Jason

Note = that the wavefunction =CE=A8 is commonly described with the help of = chosen "basis orbitals" {=CF=87k} (such as those of a 6-311++G** = basis set, as employed in numerical work described below). However, for = given =CE=A8 the solutions of Eq. (1) are in principleindependent of the chosen basis orbitals, whether of = Slater, Gaussian, or plane wave type. Indeed, the NOs and associated = orbital-based concepts remain rigorously defined by Eq. (1) even if =CE=A8= is specified only in interparticle (Hylleraas or James-Coolidge = typerij) coordinates, without reference = to any orbital basis set whatsoever. While it is often numerically = convenient to employ basis orbitals (orthogonal or non-orthogonal) to = solve eigenvalue problems such as Eq. (1), it is important to realize = that the eigenorbitals =CE=98k are in = principle independent of the particular basis = orbitals chosen. Natural orbitals =CE=98k are intrinsic and unique to =CE=A8, whereas basis orbitals = =CF=87k are non-unique "fitting" = functions, chosen merely for numerical = convenience.


On Feb 11, 2014, = at 3:56 AM, Peeter Burk peeter.burk,ut.ee <owner-chemistry : ccl.net> = wrote:


Sent to CCL by: Peeter Burk = [peeter.burk[]ut.ee]
Can you provide the reference to the "proof" = that NBO charges are basis set dependent? My limited knowledge (based on = e.g. Jensen's Introduction to comp. chem.) is that NBO charges are not = sensitive to the size of basis set...

By the way, my favourite = paper on atomic charges is

PRINCIPAL COMPONENTS OF = IONICITY
By: MEISTER, J; SCHWARZ, WHE
JOURNAL OF PHYSICAL = CHEMISTRY  Volume: 98   Issue: 33   Pages: = 8245-8252

which compares atomic charges calculated by 25 = different schemes and states that "Only a single principal component of = ionicity has been found...". By ionicity the authors mean atomic = charges.

Best regards
Peeter

On 02/11/2014 11:12 AM, = Susi Lehtola susi.lehtola]![alumni.helsinki.fi = wrote:
NBO charges are explicitly dependent = on the basis set, like Mulliken
and L=C3=B6wdin.

AIM charges = are not, but then again according to them e.g. H2O and HCN
are = ionic...

Probably the best scheme is something like the recently = proposed
iterative Hirshfeld schemes, but I'm not aware of any = program that
implements these.

Another possibility are = electrostatic potential charges, which are
available in e.g. = Gaussian.




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<= br>= --Apple-Mail=_E25EC531-7A2B-4162-8AA1-9101D8F4CF43-- From owner-chemistry@ccl.net Tue Feb 11 14:36:00 2014 From: "Sebastian Kozuch seb.kozuch!A!gmail.com" To: CCL Subject: CCL:G: Converges using HF and hybrid DFT, but fails to converge using pure DFT Message-Id: <-49664-140211125756-19084-pH/YGJAQbWXcFxQLiDZ8qQ[*]server.ccl.net> X-Original-From: Sebastian Kozuch Content-Transfer-Encoding: 7bit Content-Type: text/plain; charset=ISO-8859-1; format=flowed Date: Tue, 11 Feb 2014 11:57:34 -0600 MIME-Version: 1.0 Sent to CCL by: Sebastian Kozuch [seb.kozuch(a)gmail.com] That happens sometimes. Pure GGA have some extra convergence difficulties. You may try to take the converged orbitals in the checkpoint file from a hybrid DFT and use them as a guess for the GGA, and try with scf(qc) or scf(xqc). More expensive, but life is always more expensive than our expectations. Best, Sebastian On 2/11/2014 10:00 AM, Dr. Vitaly Chaban vvchaban[#]gmail.com wrote: > Sent to CCL by: "Dr. Vitaly Chaban" [vvchaban__gmail.com] > Dear All - > > The wavefunction for the system consisting of 2nd and 3rd row elements > converges (at least to 10^(-7) Ha) using HF and hybrid DFT with modest > basis set, but it does not converge appropriately (converges only to > 10^(-4) Ha) using pure DFT functionals. The geometry is close to > minimum, the cheap solutions, such as VShift, NoVarAcc, Guess=Read do > not work. > > Which keyword(s) in Gaussian'09 would you suggest to enhance the SCF > convergence in this case? > > > Dr. Vitaly V. Chaban> > -- 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 Tue Feb 11 15:12:00 2014 From: "Ol Ga eurisco1=pochta.ru" To: CCL Subject: CCL:G: Converges using HF and hybrid DFT, but fails to converge using pure DF Message-Id: <-49665-140211142703-30558-EyKEL0Uy92B9fDZaKfwoew[a]server.ccl.net> X-Original-From: "Ol Ga" Date: Tue, 11 Feb 2014 14:27:01 -0500 Sent to CCL by: "Ol Ga" [eurisco1|,|pochta.ru] Dear Dr. Vitaly V. Chaban, I would suggest to use xqc and/or Fermi keywords in the SCF group. I guess, XQC is the most helpful in these cases. BTW, it is possible that it is an excited electronic state. Thus, it may cause this problem. I hope, it is helpful. Sincerely, Ol Ga ----- ----- > From: Dr. Vitaly Chaban vvchaban[#]gmail.com Sent: Tuesday, February 11, 2014 8:00 PM To: Ga, Ol Subject: CCL:G: Converges using HF and hybrid DFT, but fails to converge using pure DFT Sent to CCL by: "Dr. Vitaly Chaban" [vvchaban__gmail.com] Dear All - The wavefunction for the system consisting of 2nd and 3rd row elements converges (at least to 10^(-7) Ha) using HF and hybrid DFT with modest basis set, but it does not converge appropriately (converges only to 10^(-4) Ha) using pure DFT functionals. The geometry is close to minimum, the cheap solutions, such as VShift, NoVarAcc, Guess=Read do not work. Which keyword(s) in Gaussian'09 would you suggest to enhance the SCF convergence in this case? Dr. Vitaly V. Chabanhttp://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 Feb 11 15:46:01 2014 From: "Christopher Cramer cramer.+*+.umn.edu" To: CCL Subject: CCL:G: How to consider charge on particular atom -lithium Message-Id: <-49666-140211150951-14321-lCr7hqhqnzmHOvDyivjsFA+*+server.ccl.net> X-Original-From: Christopher Cramer Content-Transfer-Encoding: 8bit Content-Type: text/plain; charset=windows-1252 Date: Tue, 11 Feb 2014 14:09:36 -0600 Mime-Version: 1.0 (Mac OS X Mail 7.1 \(1827\)) Sent to CCL by: Christopher Cramer [cramer]_[umn.edu] Tried to hold out, but irresistibly drawn into the fray. Partial charges? Ahem. CM5. Described at http://pubs.acs.org/doi/abs/10.1021/ct200866d (CM5 is a mapped Hirshfeld model; the paper above includes comparison to the iterative Hirshfeld model) Bill Jorgensen’s group has found them particularly effective for explicit simulations of solutes in condensed phases (http://www.cecam.org/workshop-4-901.html?presentation_id=11050) Implemented in most up-to-date Gaussian — also in Q-Chem, I believe. Free “app” (CM5PAC) to generate CM5 charges from older versions of Gaussian09 at http://comp.chem.umn.edu/cm5pac/ Chris -- Christopher J. Cramer Elmore H. Northey Professor and Associate Dean for Academic Affairs University of Minnesota Department of Chemistry and College of Science & Engineering Minneapolis, MN 55455-0431 Phone: (612) 624-0859 (Chemistry) Phone: (612) 624-9371 (CSE) -------------------------- Mobile: (952) 297-2575 Email: cramer[-]umn.edu Twitter: [-]ChemProfCramer Website: http://pollux.chem.umn.edu From owner-chemistry@ccl.net Tue Feb 11 16:21:00 2014 From: "Bennion, Brian Bennion1^^^llnl.gov" To: CCL Subject: CCL:G: How to consider charge on particular atom -lithium Message-Id: <-49667-140211142842-31943-WD0jZwY/6s5Fx0ZPoiEPeg{:}server.ccl.net> X-Original-From: "Bennion, Brian" Content-Language: en-US Content-Transfer-Encoding: 8bit Content-Type: text/plain; charset="us-ascii" Date: Tue, 11 Feb 2014 19:28:32 +0000 MIME-Version: 1.0 Sent to CCL by: "Bennion, Brian" [Bennion1*_*llnl.gov] Hello, The quoted reference is off by 1 year, it should read 2012. Brian -----Original Message----- > From: owner-chemistry+bennion1==llnl.gov|a|ccl.net [mailto:owner-chemistry+bennion1==llnl.gov|a|ccl.net] On Behalf Of Tian Lu sobereva-x-sina.com Sent: Tuesday, February 11, 2014 7:09 AM To: Bennion, Brian Subject: CCL:G: How to consider charge on particular atom -lithium Sent to CCL by: "Tian Lu" [sobereva/./sina.com] Hi, AFAIK, there is only one public program can realize Hirshfeld-I, namely HiPart (http://molmod.ugent.be/software/). Another modified Hirshfeld-based method alternative to Hirshfeld-I is atomic dipole moment corrected Hirshfeld (ADCH) population method, which is the one I highly recommend, see J. Theor. Comp. Chem., 2012, 11: 163-183. ADCH charges have much better reproducibility for electrostatic potential than Hirshfeld charges, and the molecular dipole moment can be even exactly reproduced. ADCH has been implemented in Multiwfn program (http://Multiwfn.codeplex.com, see Section 4.7.2 of its manual for example). NPA charges (also known as NBO charges) are also nice choice. In fact they are not explicitly dependent on but only indirectly dependent on the basis-set, because the original basis functions will be first transformed to natural atomic orbitals before performing natural population analysis, this step conspicuously reduces the sensitivity of NPA charges to basis-set. According to my experiences, the relative sensitivity to basis-set is Mulliken>=Lowdin>>NPAAIMcharges by fitting ESP (MK,CHELPG,etc.) >= HirshfeldADCH. Personally I don't recommend using AIM charges, since calculating AIM charges is usually time-consuming, and their reproducibility for observable quantities are quite poor. A comprehensive comparison of atomic charges can be found in Acta Phys.-Chim. Sinica, 2011, 28: 1-18 (http://www.whxb.pku.edu.cn/EN/abstract/abstract27818.shtml) Tian Lu ----- Original Message ----- > From: "Susi Lehtola susi.lehtola]![alumni.helsinki.fi" > To: "Lu, Tian " Subject: CCL:G: How to consider charge on particular atom -lithium Date: 2014-02-11 17:12 Sent to CCL by: Susi Lehtola [susi.lehtola-.-alumni.helsinki.fi] On Mon, 10 Feb 2014 18:37:44 -0500 "Jim Kress ccl_nospam_._kressworks.com" wrote: > Sent to CCL by: "Jim Kress" [ccl_nospam,kressworks.com] AIM and NBO > charges would be the best choice. Mulliken and Lowdin are far too basis set dependent. NBO charges are explicitly dependent on the basis set, like Mulliken and Lwdin. AIM charges are not, but then again according to them e.g. H2O and HCN are ionic... Probably the best scheme is something like the recently proposed iterative Hirshfeld schemes, but I'm not aware of any program that implements these. Another possibility are electrostatic potential charges, which are available in e.g. Gaussian. -- --------------------------------------------------------------- Mr. Susi Lehtola, PhD Research Associate susi.lehtola%a%alumni.helsinki.fi Department of Applied Physics http://www.helsinki.fi/~jzlehtol Aalto University Finland --------------------------------------------------------------- Susi Lehtola, FT Tutkijatohtori susi.lehtola%a%alumni.helsinki.fi Fysiikan laitos http://www.helsinki.fi/~jzlehtol Aalto-yliopistohttp://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 Feb 11 16:56:01 2014 From: "Salter-Duke, Brian James - brian.james.duke##gmail.com" To: CCL Subject: CCL:G: How to consider charge on particular atom -lithium Message-Id: <-49668-140211154947-17736-TL7fmqAOlz/iGNJ0A+nVDw\a/server.ccl.net> X-Original-From: "Salter-Duke, Brian James -" Content-Disposition: inline Content-Type: text/plain; charset=us-ascii Date: Wed, 12 Feb 2014 07:49:29 +1100 MIME-Version: 1.0 Sent to CCL by: "Salter-Duke, Brian James -" [brian.james.duke-x-gmail.com] I do not want to address how the various methods work in practice, as I do not have the experience. I do however want to make a general point and then ask a question. Mulliken charges are not basis set independent as they depend on the basis functions we happen to use on each atom. As another poster commented, if we use a one centre complete basis the method puts all the charge on that atom. Long ago there was a set of one-centre expansion calculations on simple systems such as methane. There are no basis functions on the hydrogen atoms. The Mulliken charges are C(4-) and H(+). If we used basis functions centered only on the H atoms we would get C(4+) and H(-). Mulliken charges do not have a basis set limit. Too often we use methods to interpret wave functions that do not have a basis set limit. I suggest we stop doing that and use methods that do, just as we have energies that do. We often extrapolate to that energy limit and we should extrapolate to limits for other properties, even when they are not observable properties such as charges. As others have shown many other methods can reduce the sensitivity of NPA charges to basis-set, but they still do not properly have a basis set limit. Bader charges depend on the basis set only in the sense that the density depends on the basis set. They do have a proper basis set limit. They are obtained by defining the boundaries of each atom and then integrating over the atoms. The AIM method of getting those boundaries seems soundly based. Nobody, I think, has come up with a better method. So why are Bader charges thought to be so bad and unacceptable. Has that question been properly considered and analysed? Brian Duke. On Tue, Feb 11, 2014 at 10:09:02AM -0500, Tian Lu sobereva-x-sina.com wrote: > > Sent to CCL by: "Tian Lu" [sobereva/./sina.com] > Hi, > > AFAIK, there is only one public program can realize Hirshfeld-I, namely HiPart (http://molmod.ugent.be/software/). > Another modified Hirshfeld-based method alternative to Hirshfeld-I is > atomic dipole moment corrected Hirshfeld (ADCH) population method, > which is the one I highly recommend, see J. Theor. Comp. Chem., 2012, > 11: 163-183. ADCH charges have much better reproducibility for > electrostatic potential than Hirshfeld charges, and the molecular > dipole moment can be even exactly reproduced. ADCH has been > implemented in Multiwfn program (http://Multiwfn.codeplex.com, see > Section 4.7.2 of its manual for example). > NPA charges (also known as NBO charges) are also nice choice. In fact > they are not explicitly dependent on but only indirectly dependent on > the basis-set, because the original basis functions will be first > transformed to natural atomic orbitals before performing natural > population analysis, this step conspicuously reduces the sensitivity > of NPA charges to basis-set. According to my experiences, the relative > sensitivity to basis-set is Mulliken>=Lowdin>>NPAAIMcharges by fitting > ESP (MK,CHELPG,etc.) >= HirshfeldADCH. > Personally I don't recommend using AIM charges, since calculating AIM > charges is usually time-consuming, and their reproducibility for > observable quantities are quite poor. > A comprehensive comparison of atomic charges can be found in Acta > Phys.-Chim. Sinica, 2011, 28: 1-18 > (http://www.whxb.pku.edu.cn/EN/abstract/abstract27818.shtml) > > Tian Lu > > > > > ----- Original Message ----- > > From: "Susi Lehtola susi.lehtola]![alumni.helsinki.fi" > To: "Lu, Tian " > Subject: CCL:G: How to consider charge on particular atom -lithium > Date: 2014-02-11 17:12 > > > > Sent to CCL by: Susi Lehtola [susi.lehtola-.-alumni.helsinki.fi] > On Mon, 10 Feb 2014 18:37:44 -0500 > "Jim Kress ccl_nospam_._kressworks.com" wrote: > > Sent to CCL by: "Jim Kress" [ccl_nospam,kressworks.com] > > AIM and NBO charges would be the best choice. Mulliken and Lowdin are far too basis set dependent. > NBO charges are explicitly dependent on the basis set, like Mulliken > and Lwdin. > AIM charges are not, but then again according to them e.g. H2O and HCN > are ionic... > Probably the best scheme is something like the recently proposed > iterative Hirshfeld schemes, but I'm not aware of any program that > implements these. > Another possibility are electrostatic potential charges, which are > available in e.g. Gaussian. > -- > --------------------------------------------------------------- > Mr. Susi Lehtola, PhD Research Associate > susi.lehtola%a%alumni.helsinki.fi Department of Applied Physics > http://www.helsinki.fi/~jzlehtol Aalto University > Finland > --------------------------------------------------------------- > Susi Lehtola, FT Tutkijatohtori > susi.lehtola%a%alumni.helsinki.fi Fysiikan laitos > http://www.helsinki.fi/~jzlehtol Aalto-yliopisto> -- Brian Salter-Duke (Brian Duke) Brian.Salter-Duke[a]monash.edu Adjunct Associate Professor Monash Institute of Pharmaceutical Sciences Monash University Parkville Campus, VIC 3052, Australia From owner-chemistry@ccl.net Tue Feb 11 17:31:00 2014 From: "Dr. Vitaly Chaban vvchaban::gmail.com" To: CCL Subject: CCL:G: Converges using HF and hybrid DFT, but fails to converge using pure DFT Message-Id: <-49669-140211172848-6841-95JepoXYlM8UaMVAoewMww||server.ccl.net> X-Original-From: "Dr. Vitaly Chaban" Content-Type: text/plain; charset=ISO-8859-1 Date: Tue, 11 Feb 2014 23:28:01 +0100 MIME-Version: 1.0 Sent to CCL by: "Dr. Vitaly Chaban" [vvchaban/./gmail.com] On Tue, Feb 11, 2014 at 6:57 PM, Sebastian Kozuch seb.kozuch!A!gmail.com wrote: > > Sent to CCL by: Sebastian Kozuch [seb.kozuch(a)gmail.com] > That happens sometimes. Pure GGA have some extra convergence difficulties. > You may try to take the converged orbitals in the checkpoint file from a > hybrid DFT and use them as a guess for the GGA, and try with scf(qc) or > scf(xqc). More expensive, but life is always more expensive than our > expectations. The bad thing is that even SCF=QC with Guess=Read does not work adequately. Below follows the logfile after a couple of hours of iterations. The guess came from "B3LYP/CEP-31G* SCF=Conver=9", and the failed convergence example used "BLYP/CEP-31G*" Unless there is no other magic way, I will have to decrease the SCF criterion down to what BLYP can afford. Maybe indeed a bit exotic system... ======================================== Initial guess from the checkpoint file: "tst.chk" B after Tr= 0.138569 0.004861 0.143222 Rot= -0.322975 0.086443 0.861545 -0.382041 Ang= 217.69 deg. Rare condition: small coef for last iteration: 0.000D+00 EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations Rare condition: small coef for last iteration: -0.546D-15 EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations Rare condition: small coef for last iteration: 0.763D-15 EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations Rare condition: small coef for last iteration: -0.133D-14 EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations Rare condition: small coef for last iteration: -0.379D-15 EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations Rare condition: small coef for last iteration: -0.523D-15 EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations Rare condition: small coef for last iteration: -0.114D-14 EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations Rare condition: small coef for last iteration: 0.165D-14 EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations Rare condition: small coef for last iteration: -0.350D-15 EnCoef did 100 forward-backward iterations Restarting incremental Fock formation. EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 55 forward-backward iterations Rare condition: small coef for last iteration: -0.222D-15 EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations Restarting incremental Fock formation. EnCoef did 100 forward-backward iterations EnCoef did 74 forward-backward iterations Rare condition: small coef for last iteration: 0.777D-15 EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 75 forward-backward iterations Rare condition: small coef for last iteration: -0.666D-15 EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations Restarting incremental Fock formation. EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations >>>>>>>>>> Convergence criterion not met. SCF Done: E(RB-LYP) = -477.317424055 A.U. after 65 cycles NFock= 64 Conv=0.47D-05 -V/T= 2.4474 Accept linear search using points 1 and 2. Accept linear search using points 5 and 6. Minimum is close to point 6 DX= -1.72D-01 DF= -7.90D-03 DXR= 9.98D-02 DFR= 9.09D-03 which will be used. Minimum is close to point 3 DX= -4.36D-03 DF= -1.04D-04 DXR= 1.47D-02 DFR= 2.17D-04 which will be used. Accept linear search using points 1 and 2. Restarting incremental Fock formation. Minimum is close to point 3 DX= -9.41D-03 DF= -2.94D-05 DXR= 1.92D-02 DFR= 2.99D-04 which will be used. Accept linear search using points 1 and 2. Minimum is close to point 3 DX= 1.48D-02 DF= -2.10D-05 DXR= 2.41D-02 DFR= 5.73D-04 which will be used. Accept linear search using points 1 and 2. Accept linear search using points 1 and 2. Minimum is close to point 3 DX= 6.60D-03 DF= -5.11D-06 DXR= 1.62D-02 DFR= 2.77D-04 which will be used. Accept linear search using points 1 and 2. Restarting incremental Fock formation. Minimum is close to point 4 DX= 8.51D-02 DF= -3.98D-05 DXR= 7.84D-02 DFR= 6.13D-03 which will be used. Accept linear search using points 1 and 2. Accept linear search using points 1 and 2. Accept linear search using points 2 and 3. ======================================== Dr. Vitaly V. Chaban > Best, > Sebastian > > On 2/11/2014 10:00 AM, Dr. Vitaly Chaban vvchaban[#]gmail.com wrote: >> >> Sent to CCL by: "Dr. Vitaly Chaban" [vvchaban__gmail.com] >> Dear All - >> >> The wavefunction for the system consisting of 2nd and 3rd row elements >> converges (at least to 10^(-7) Ha) using HF and hybrid DFT with modest >> basis set, but it does not converge appropriately (converges only to >> 10^(-4) Ha) using pure DFT functionals. The geometry is close to >> minimum, the cheap solutions, such as VShift, NoVarAcc, Guess=Read do >> not work. >> >> Which keyword(s) in Gaussian'09 would you suggest to enhance the SCF >> convergence in this case? >> >> >> Dr. Vitaly V. Chaban> >> > > > -- > xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx > ..........Sebastian Kozuch........... > xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx > ......University of North Texas...... > ..........Denton, Texas, USA......... > ........ seb.kozuch*o*gmail.com ....... > http://yfaat.ch.huji.ac.il/kozuch.htm > xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxhttp://www.ccl.net/chemistry/sub_unsub.shtmlConferences: > http://server.ccl.net/chemistry/announcements/conferences/> > From owner-chemistry@ccl.net Tue Feb 11 19:19:00 2014 From: "Mikael Johansson mikael.johansson~~iki.fi" To: CCL Subject: CCL:G: Converges using HF and hybrid DFT, but fails to converge using pure DFT Message-Id: <-49670-140211191046-31606-ZZWtjMvaMC2iunvlNxEfXg*o*server.ccl.net> X-Original-From: Mikael Johansson Content-Type: text/plain; charset=US-ASCII; format=flowed Date: Wed, 12 Feb 2014 02:10:35 +0200 (EET) MIME-Version: 1.0 Sent to CCL by: Mikael Johansson [mikael.johansson~!~iki.fi] Hello Vitaly and All, On Tue, 11 Feb 2014, Dr. Vitaly Chaban vvchaban::gmail.com wrote: > Unless there is no other magic way, I will have to decrease the SCF > criterion down to what BLYP can afford. Maybe indeed a bit exotic > system... > >>>>>>>>>> Convergence criterion not met. > SCF Done: E(RB-LYP) = -477.317424055 A.U. after 65 cycles > NFock= 64 Conv=0.47D-05 -V/T= 2.4474 You might have to decrease the convergence criterion, yes, but the above solution is not acceptable as the virial theorem is far from fulfilled (-V/T should be (very close to) two). If hybrids and HF converge, but pure GGAs don't, I suspect your problem is a negative or very small HOMO-LUMO gap at the GGA level. Many programs have real difficulty in converging systems like that with default settings. I'm no Gaussian expert, so I don't know if it automatically changes orbital occupations/orderings during SCF according to the aufbau principle. If it does, switch that off with some magic keyword. Also try, after restarting from hybrid GGA orbitals, to increase the level-shift between occupied and virtual orbitals. Good luck, Mikael J. http://www.iki.fi/~mpjohans/ From owner-chemistry@ccl.net Tue Feb 11 20:06:00 2014 From: "Chang, Christopher Christopher.Chang,,nrel.gov" To: CCL Subject: CCL:G: Converges using HF and hybrid DFT, but fails to converge using pure DFT Message-Id: <-49671-140211200337-7205-nalq3sTYQXYtGpebVF+Wog-#-server.ccl.net> X-Original-From: "Chang, Christopher" Content-Language: en-US Content-Transfer-Encoding: 8bit Content-Type: text/plain; charset="us-ascii" Date: Tue, 11 Feb 2014 18:03:13 -0700 MIME-Version: 1.0 Sent to CCL by: "Chang, Christopher" [Christopher.Chang#,#nrel.gov] One approach you might try, since you are going from B3LYP (20% orbital-dependent exchange) to BLYP (0% ODE, but otherwise the same) is to dial down manually the percentage of ODE in smaller increments, and observe how orbital energies are changing around the HOMO-LUMO gap. If it looks like 2+ near-frontier orbitals might change order as you decrease ODE, you might try swapping the appropriate orbitals in your initial B3LYP guess prior to running the BLYP SCF. -----Original Message----- > From: owner-chemistry+christopher.chang==nrel.gov{}ccl.net [mailto:owner-chemistry+christopher.chang==nrel.gov{}ccl.net] On Behalf Of Dr. Vitaly Chaban vvchaban::gmail.com Sent: Tuesday, February 11, 2014 3:28 PM To: Chang, Christopher Subject: CCL:G: Converges using HF and hybrid DFT, but fails to converge using pure DFT Sent to CCL by: "Dr. Vitaly Chaban" [vvchaban/./gmail.com] On Tue, Feb 11, 2014 at 6:57 PM, Sebastian Kozuch seb.kozuch!A!gmail.com wrote: > > Sent to CCL by: Sebastian Kozuch [seb.kozuch(a)gmail.com] That happens > sometimes. Pure GGA have some extra convergence difficulties. > You may try to take the converged orbitals in the checkpoint file from > a hybrid DFT and use them as a guess for the GGA, and try with scf(qc) > or scf(xqc). More expensive, but life is always more expensive than > our expectations. The bad thing is that even SCF=QC with Guess=Read does not work adequately. Below follows the logfile after a couple of hours of iterations. The guess came from "B3LYP/CEP-31G* SCF=Conver=9", and the failed convergence example used "BLYP/CEP-31G*" Unless there is no other magic way, I will have to decrease the SCF criterion down to what BLYP can afford. Maybe indeed a bit exotic system... ======================================== Initial guess from the checkpoint file: "tst.chk" B after Tr= 0.138569 0.004861 0.143222 Rot= -0.322975 0.086443 0.861545 -0.382041 Ang= 217.69 deg. Rare condition: small coef for last iteration: 0.000D+00 EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations Rare condition: small coef for last iteration: -0.546D-15 EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations Rare condition: small coef for last iteration: 0.763D-15 EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations Rare condition: small coef for last iteration: -0.133D-14 EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations Rare condition: small coef for last iteration: -0.379D-15 EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations Rare condition: small coef for last iteration: -0.523D-15 EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations Rare condition: small coef for last iteration: -0.114D-14 EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations Rare condition: small coef for last iteration: 0.165D-14 EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations Rare condition: small coef for last iteration: -0.350D-15 EnCoef did 100 forward-backward iterations Restarting incremental Fock formation. EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 55 forward-backward iterations Rare condition: small coef for last iteration: -0.222D-15 EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations Restarting incremental Fock formation. EnCoef did 100 forward-backward iterations EnCoef did 74 forward-backward iterations Rare condition: small coef for last iteration: 0.777D-15 EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 75 forward-backward iterations Rare condition: small coef for last iteration: -0.666D-15 EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations Restarting incremental Fock formation. EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations EnCoef did 100 forward-backward iterations >>>>>>>>>> Convergence criterion not met. SCF Done: E(RB-LYP) = -477.317424055 A.U. after 65 cycles NFock= 64 Conv=0.47D-05 -V/T= 2.4474 Accept linear search using points 1 and 2. Accept linear search using points 5 and 6. Minimum is close to point 6 DX= -1.72D-01 DF= -7.90D-03 DXR= 9.98D-02 DFR= 9.09D-03 which will be used. Minimum is close to point 3 DX= -4.36D-03 DF= -1.04D-04 DXR= 1.47D-02 DFR= 2.17D-04 which will be used. Accept linear search using points 1 and 2. Restarting incremental Fock formation. Minimum is close to point 3 DX= -9.41D-03 DF= -2.94D-05 DXR= 1.92D-02 DFR= 2.99D-04 which will be used. Accept linear search using points 1 and 2. Minimum is close to point 3 DX= 1.48D-02 DF= -2.10D-05 DXR= 2.41D-02 DFR= 5.73D-04 which will be used. Accept linear search using points 1 and 2. Accept linear search using points 1 and 2. Minimum is close to point 3 DX= 6.60D-03 DF= -5.11D-06 DXR= 1.62D-02 DFR= 2.77D-04 which will be used. Accept linear search using points 1 and 2. Restarting incremental Fock formation. Minimum is close to point 4 DX= 8.51D-02 DF= -3.98D-05 DXR= 7.84D-02 DFR= 6.13D-03 which will be used. Accept linear search using points 1 and 2. Accept linear search using points 1 and 2. Accept linear search using points 2 and 3. ======================================== Dr. Vitaly V. Chaban > Best, > Sebastian > > On 2/11/2014 10:00 AM, Dr. Vitaly Chaban vvchaban[#]gmail.com wrote: >> >> Sent to CCL by: "Dr. Vitaly Chaban" [vvchaban__gmail.com] Dear All - >> >> The wavefunction for the system consisting of 2nd and 3rd row >> elements converges (at least to 10^(-7) Ha) using HF and hybrid DFT >> with modest basis set, but it does not converge appropriately >> (converges only to >> 10^(-4) Ha) using pure DFT functionals. The geometry is close to >> minimum, the cheap solutions, such as VShift, NoVarAcc, Guess=Read do >> not work. >> >> Which keyword(s) in Gaussian'09 would you suggest to enhance the SCF >> convergence in this case? >> >> >> Dr. Vitaly V. Chaban> >> > > > -- > xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx > ..........Sebastian Kozuch........... > xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx > ......University of North Texas...... > ..........Denton, Texas, USA......... > ........ seb.kozuch*o*gmail.com ....... > http://yfaat.ch.huji.ac.il/kozuch.htm > xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxhttp://www.ccl.net/chemistry/sub_unsub.shtmlConferences: > http://server.ccl.net/chemistry/announcements/conferences/http://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 Feb 11 20:44:00 2014 From: "Christopher Cramer cramer%x%umn.edu" To: CCL Subject: CCL:G: How to consider charge on particular atom -lithium Message-Id: <-49672-140211183136-22161-Tixf4Kam84fPqpXBXzr6kg{:}server.ccl.net> X-Original-From: Christopher Cramer Content-Transfer-Encoding: 8bit Content-Type: text/plain; charset=windows-1252 Date: Tue, 11 Feb 2014 17:31:22 -0600 Mime-Version: 1.0 (Mac OS X Mail 7.1 \(1827\)) Sent to CCL by: Christopher Cramer [cramer**umn.edu] Brian, Sure, I can take a run at your final question. The “problem” with Bader charges is not that there is any lack of elegance in the definition of the atomic basins, nor that they have a complete basis set limit (surely a good thing!) The problem is that we usually want partial atomic charges to do the best job possible of representing the molecular charge distribution with a set of atom-centered monopoles, but there may be rather large HIGHER moments of the charge within the Bader atomic basins (i.e., beyond the difference in total number of electrons integrated over the Bader atom subtracted from the nuclear charge). When that happens, collapsing all those electrons entirely on the nuclear position, about which they are not symmetrically disposed, can lead to rather bizarre charges. A good example that I recall from many years ago was work of Rainer Glaser at Missouri. He showed that diazonium cations (i.e., RN2+ structures) would show enormous variation in the two different N charges with seemingly tiny variations in R (e.g., going from methyl to ethyl). The problem is that LOTS of the electronic charge is built up about midway between the two N atoms, but the zero-flux surface is VERY sensitive to the substituent. So, a small movement of the zero-flux surface to one side or the other suddenly moves a sizable fraction of an electron from one N “atom” to the other. Of course, the ACTUAL charge distribution is actually only very slightly perturbed, and if one were to consider the atomic dipole moments within the basins, one would see that their variations largely cancel the changes in the monopoles, but we aren’t usually interested in using higher atomic moments when we’re looking for partial atomic charges — we’re hoping for a simpler representation. So much is written on partial atomic charges that I won’t indulge my otherwise dangerous proclivity to lecture, but I thought I’d at least address your question of why Bader charges tend to find little use in communities not interested in considering higher moments of the atomic basin charge distributions as well. Best, Chris On Feb 11, 2014, at 14:49, Salter-Duke, Brian James brian.james.duke##gmail.com wrote: > > Sent to CCL by: "Salter-Duke, Brian James " [brian.james.duke-x-gmail.com] > I do not want to address how the various methods work in practice, as I > do not have the experience. I do however want to make a general point > and then ask a question. > > Mulliken charges are not basis set independent as they depend on the > basis functions we happen to use on each atom. As another poster > commented, if we use a one centre complete basis the method puts all the > charge on that atom. Long ago there was a set of one-centre expansion > calculations on simple systems such as methane. There are no basis > functions on the hydrogen atoms. The Mulliken charges are C(4-) and > H(+). If we used basis functions centered only on the H atoms we would > get C(4+) and H(-). Mulliken charges do not have a basis set limit. Too > often we use methods to interpret wave functions that do not have a > basis set limit. I suggest we stop doing that and use methods that do, > just as we have energies that do. We often extrapolate to that energy > limit and we should extrapolate to limits for other properties, even > when they are not observable properties such as charges. > > As others have shown many other methods can reduce the sensitivity of > NPA charges to basis-set, but they still do not properly have a basis > set limit. > > Bader charges depend on the basis set only in the sense that the density > depends on the basis set. They do have a proper basis set limit. They > are obtained by defining the boundaries of each atom and then > integrating over the atoms. The AIM method of getting those boundaries > seems soundly based. Nobody, I think, has come up with a better method. > So why are Bader charges thought to be so bad and unacceptable. Has that > question been properly considered and analysed? > > Brian Duke. > > On Tue, Feb 11, 2014 at 10:09:02AM -0500, Tian Lu sobereva-x-sina.com wrote: >> >> Sent to CCL by: "Tian Lu" [sobereva/./sina.com] >> Hi, >> >> AFAIK, there is only one public program can realize Hirshfeld-I, namely HiPart (http://molmod.ugent.be/software/). > >> Another modified Hirshfeld-based method alternative to Hirshfeld-I is >> atomic dipole moment corrected Hirshfeld (ADCH) population method, >> which is the one I highly recommend, see J. Theor. Comp. Chem., 2012, >> 11: 163-183. ADCH charges have much better reproducibility for >> electrostatic potential than Hirshfeld charges, and the molecular >> dipole moment can be even exactly reproduced. ADCH has been >> implemented in Multiwfn program (http://Multiwfn.codeplex.com, see >> Section 4.7.2 of its manual for example). > >> NPA charges (also known as NBO charges) are also nice choice. In fact >> they are not explicitly dependent on but only indirectly dependent on >> the basis-set, because the original basis functions will be first >> transformed to natural atomic orbitals before performing natural >> population analysis, this step conspicuously reduces the sensitivity >> of NPA charges to basis-set. According to my experiences, the relative >> sensitivity to basis-set is Mulliken>=Lowdin>>NPAAIMcharges by fitting >> ESP (MK,CHELPG,etc.) >= HirshfeldADCH. > >> Personally I don't recommend using AIM charges, since calculating AIM >> charges is usually time-consuming, and their reproducibility for >> observable quantities are quite poor. > >> A comprehensive comparison of atomic charges can be found in Acta >> Phys.-Chim. Sinica, 2011, 28: 1-18 >> (http://www.whxb.pku.edu.cn/EN/abstract/abstract27818.shtml) > >> >> Tian Lu >> >> >> >> >> ----- Original Message ----- >>> From: "Susi Lehtola susi.lehtola]![alumni.helsinki.fi" >> To: "Lu, Tian " >> Subject: CCL:G: How to consider charge on particular atom -lithium >> Date: 2014-02-11 17:12 >> >> >> >> Sent to CCL by: Susi Lehtola [susi.lehtola-.-alumni.helsinki.fi] >> On Mon, 10 Feb 2014 18:37:44 -0500 >> "Jim Kress ccl_nospam_._kressworks.com" wrote: >>> Sent to CCL by: "Jim Kress" [ccl_nospam,kressworks.com] >>> AIM and NBO charges would be the best choice. Mulliken and Lowdin are far too basis set dependent. >> NBO charges are explicitly dependent on the basis set, like Mulliken >> and Lwdin. >> AIM charges are not, but then again according to them e.g. H2O and HCN >> are ionic... >> Probably the best scheme is something like the recently proposed >> iterative Hirshfeld schemes, but I'm not aware of any program that >> implements these. >> Another possibility are electrostatic potential charges, which are >> available in e.g. Gaussian. >> -- >> --------------------------------------------------------------- >> Mr. Susi Lehtola, PhD Research Associate >> susi.lehtola%a%alumni.helsinki.fi Department of Applied Physics >> http://www.helsinki.fi/~jzlehtol Aalto University >> Finland >> --------------------------------------------------------------- >> Susi Lehtola, FT Tutkijatohtori >> susi.lehtola%a%alumni.helsinki.fi Fysiikan laitos >> http://www.helsinki.fi/~jzlehtol Aalto-yliopisto> > > -- > Brian Salter-Duke (Brian Duke) Brian.Salter-Duke|monash.edu > Adjunct Associate Professor > Monash Institute of Pharmaceutical Sciences > Monash University Parkville Campus, VIC 3052, Australia> > -- Christopher J. Cramer Elmore H. Northey Professor and Associate Dean for Academic Affairs University of Minnesota Department of Chemistry and College of Science & Engineering Minneapolis, MN 55455-0431 Phone: (612) 624-0859 (Chemistry) Phone: (612) 624-9371 (CSE) -------------------------- Mobile: (952) 297-2575 Email: cramer.{:}.umn.edu Twitter: .{:}.ChemProfCramer Website: http://pollux.chem.umn.edu