From owner-chemistry@ccl.net Fri Dec 14 08:15:00 2007 From: "John McKelvey jmmckel:-:gmail.com" To: CCL Subject: CCL: origin of ab initio Message-Id: <-35852-071214074205-9279-+P4Oqizu0q6mxmCLSFWyBQ(-)server.ccl.net> X-Original-From: "John McKelvey" Content-Type: multipart/alternative; boundary="----=_Part_766_2677250.1197636112260" Date: Fri, 14 Dec 2007 07:41:52 -0500 MIME-Version: 1.0 Sent to CCL by: "John McKelvey" [jmmckel!A!gmail.com] ------=_Part_766_2677250.1197636112260 Content-Type: text/plain; charset=ISO-8859-1 Content-Transfer-Encoding: 7bit Content-Disposition: inline Herbert's comments made me smile because I once started a Fortran/C discussion on the CCL list. Both the Fortran/C and this "ab initio" discussion [initiated accidentally with tongue in cheek remark] have brought forth some very useful information. There are always newcomers to computational chemistry who hopefully can benefit from these discussions. The accessibility of more and more computational programs and codes, particularly at little or no cost, and the seemingly ever increasing price performance of desktop and laptop PC's brings more and more people into the computational domain, and not all of these have the same background. These discussions are helpful to the less experienced, and and probably to some of us who have been around for a long time. Frankly, I still enjoy sitting in a library rereading some of the very earliest volumes of Theoretica Chimica Acta from the '60s, not unlike musicians who often go back to doing scales to limber up and refresh the mind and body. There is a lot to be learned at the pi-only PPP level. Cheers to all!! John McKelvey On Dec 14, 2007 4:38 AM, Herbert Fruchtl herbert.fruchtl~~st-andrews.ac.uk < owner-chemistry(0)ccl.net> wrote: > > Sent to CCL by: Herbert Fruchtl [herbert.fruchtl[]st-andrews.ac.uk] > This discussion is as exciting and useless as C/Fortran or vi/emacs, but > since it has started, here are my two pence worth of why using a basis > set doesn't break the "ab initio" definition, by way of an analogy. > > We know how to get to a more complete basis set. We just can't afford to > go all the way. So we choose one, and possibly a second (better) one to > check how close we are. > > We know how to do Full CI. Can't afford that either. So we stick with > some limited number of excitations, and possibly do a few test > calculations with a better method to check. > > So, if we call HF, MP2 and CCSD ab initio, we can as well call minimal > basis, vdz and vtz ab initio. There is no systematic way to make B3LYP > (in the complete basis set limit) more accurate, and this is why DFT > isn't ab initio. > > Herbert > > John McKelvey jmmckel:+:gmail.com wrote: > > Kirk, > > > > Your comment is correct with respect to construction of basis sets; > > however in any of the ZDO schemes, or other more elegant schemes, the > > choice of basis set, the choice of post-SCF treatment, or the choice of > > a DFT functional [or its construction] to get results that best > > reproduce experiment is routinely done and is either semi-empirical or > > purely empirical. Which term suits the best, I do not know. IMHO, > > "Everybody adjusts something to get the best answer." > > > > Regards, > > > > John McKelvey > > > > On Dec 12, 2007 6:59 PM, Kirk Peterson kipeters-*-wsu.edu > > > > wrote: > > > > > > Sent to CCL by: Kirk Peterson [kipeters-$-wsu.edu ] > > > > As a sidebar to this discussion, I have to strongly disagree that > > basis set parameters, exponents or contraction coefficients, > > use empirical data in their construction. All commonly used basis > > sets, even the Pople-style sets, are generated by optimizing > > exponents and contraction coefficients to minimize (ab initio) > > energies of atoms and sometimes molecules. Some of the Pople-style > > basis sets utilize scale factors to apply to atom-optimized > exponents, > > but these were based on (ab initio) molecular calculations > > and not experimental data. > > > > regards, > > > > -Kirk > > > > On Dec 12, 2007, at 8:21 AM, Rene Fournier renef+*+yorku.ca wrote: > > > > > > > > Sent to CCL by: Rene Fournier [renef\a/yorku.ca] > > > David Craig and Robert Parr first used "ab initio" in quantum > > > chemistry, > > > see > > > http://www.quantum-chemistry-history.com/Parr1.htm > > > Near the middle of that page, Parr recounts: > > > > > > " Craig and I published this paper on "configuration interaction > in > > > benzene", where we took the pi-system and did essentially a > complete > > > configuration interaction calculation on it. > > > > > > That has some trivial historical interest in that it was there > that > > > the > > > word, the term ab initio was introduced. Craig and Ross had > computed > > > everything from the start in London and I had personally computed > > > everything from start in Pittsburgh. Then we compared our answers > > > when we > > > were finished- This involved computing of all the integrals as > > best as > > > they could be done and selecting the configurations to mix for > the > > > ground > > > and exited states because there were electronic states that were > of > > > experimental interest and we checked our answers one against each > > > other > > > when we were finished. And what the paper says is, that these > > > calculations > > > were done ab initio by Craig and Ross and by me, independently. > And > > > Mulliken later said that this was the introduction of the term ab > > > initio > > > into quantum chemistry. In the short review that you have, I talk > > > about > > > this and reproduce a picture of a letter from Craig to me where > he > > > uses > > > the term ab initio in a different context. So ab initio was > > > introduced in > > > the quantum chemistry by Craig in a letter to me and I put it > > into the > > > manuscript. That's where ab initio came from. " > > > > > > > > > Funny thing is Parr later became a champion of Density Functional > > > Theory > > > and for many years (70's, 80's) DFT practitioners were often > > > criticized > > > for doing calculations that were not "ab initio". I think views > have > > > changed now; "first-principles" was introduced probably to say > > > "mostly > > > not empirical" but without the implications "ab initio" had > acquired > > > over > > > the years. The term "ab initio calculation", as it's commonly > used, > > > very rarely refers to a calculation "devoid of empiricism", for > > > example > > > the choice of basis set parameters is almost always empirical, > > > see discussion on > > > > > > http://www.ccl.net/chemistry/resources/messages/2001/11/28.002-dir/index.html > > > > > > Rene Fournier Office: 303 Petrie > > > Chemistry Dpt, York University Phone: (416) 736 2100 Ext. 30687 > > > 4700 Keele Street, Toronto FAX: (416)-736-5936 > > > Ontario, CANADA M3J 1P3 e-mail: renef*_* yorku.ca > > > > > > > > > > > On Wed, 12 Dec 2007, Christoph Etzlstorfer christoph.etzlstorfer. > > > jku.at wrote: > > > > > >> There is a story about that in Michael J.S. Dewars biography "A > > >> semiempirical life", American Chemical Society, 1992, p. 129. > > >> > > >> Best regards > > >> > > >> Christoph > > >> > > >> > > >> Am 11.12.2007 um 03:13 schrieb Tommy Ohyun Kwon ohyun.kwon _ > > >> chemistry.gatech.edu : > > >> > > >>> > > >>> Sent to CCL by: Tommy Ohyun Kwon [ohyun.kwon . > > chemistry.gatech.edu ] > > >>> Dear CCLers; > > >>> I would appreciate it if anyone could tell me who used the term > of > > >>> "ab initio > > >>> calculations" first. > > >>> Thank you very much for your kind attention. > > >>> > > >>> Best wishes, > > >>> > > >>> Tommy > > >>> > > >>> > > >>> -- > > >>> Tommy Ohyun Kwon, Ph.D > > >>> School of Chemistry and Biochemistry > > >>> Georgia Institute of Technology > > >>> Atlanta Georgia, 30332 > > >>> Email: ohyun.kwon]*[chemistry.gatech.edu > > > > >>> > > >>> > > >>> > > >>> -= This is automatically added to each message by the mailing > > >>> script =- > > >>> To recover the email address of the author of the message, > please > > >>> change> Conferences: > http://server.ccl.net/chemistry/announcements/ > > >>> conferences/ > > >>> > > >>> Search Messages: http://www.ccl.net/htdig (login: ccl, > Password: > > >>> search)> > > >>> > > >> > > >> #################################################### > > >> www.etzlstorfer.com > > > > >> *********************************************************** > > >> Dr. Christoph Etzlstorfer Phone: *43-732-2468-8750 > > >> Universitaet Linz Fax: *43-732-2468-8747 > > >> A-4040 Linz E-mail: christoph.etzlstorfer,+,jku.at > > > > >> Austria http://www.orc.uni-linz.ac.at > > >> #################################################### > > >> > > >> > > >> > > >> > > >> > > > > > > > > > > > > -= This is automatically added to each message by the mailing > script > > > =- > > > To recover the email address of the author of the message, please > > > change> Conferences: > http://server.ccl.net/chemistry/announcements/ > > > conferences/ > > > > > > Search Messages: http://www.ccl.net/htdig (login: ccl, Password: > > > search)> > > > > > > > > > > > > > > > > > > > > > E-mail to subscribers: CHEMISTRY],[ccl.net > > or use:> > > E-mail to administrators: CHEMISTRY-REQUEST],[ccl.net > > or use> > Conferences: > > http://server.ccl.net/chemistry/announcements/conferences/ > > > > > > Search Messages: http://www.ccl.net/htdig (login: ccl, Password: > > search)> > > > > > > > > -- > Herbert Fruchtl > EaStCHEM Fellow > School of Chemistry > University of St Andrews> > > ------=_Part_766_2677250.1197636112260 Content-Type: text/html; charset=ISO-8859-1 Content-Transfer-Encoding: 7bit Content-Disposition: inline Herbert's comments made me smile because I once started a Fortran/C discussion on the CCL list.  Both the Fortran/C and this "ab initio"  discussion  [initiated accidentally with tongue in cheek remark] have brought forth some very useful information.  There are always newcomers to computational chemistry who hopefully can benefit from these discussions. 

The accessibility of more and more computational programs and codes, particularly at little or no cost, and the seemingly ever increasing price performance of desktop and laptop PC's brings more and more people into the computational domain, and not all of these have the same background.  These discussions are helpful to the less experienced, and  and probably to some of us who have been around for a long time. 

Frankly, I still enjoy sitting in a library rereading  some of the very earliest volumes of Theoretica Chimica Acta from the '60s, not unlike musicians who often go back to doing scales to limber up and refresh the mind and body.  There is a lot to be learned at the pi-only PPP level.

Cheers to all!!

John McKelvey 

On Dec 14, 2007 4:38 AM, Herbert Fruchtl herbert.fruchtl~~st-andrews.ac.uk <owner-chemistry(0)ccl.net > wrote:

Sent to CCL by: Herbert Fruchtl [herbert.fruchtl[]st- andrews.ac.uk]
This discussion is as exciting and useless as C/Fortran or vi/emacs, but
since it has started, here are my two pence worth of why using a basis
set doesn't break the "ab initio" definition, by way of an analogy.

We know how to get to a more complete basis set. We just can't afford to
go all the way. So we choose one, and possibly a second (better) one to
check how close we are.

We know how to do Full CI. Can't afford that either. So we stick with
some limited number of excitations, and possibly do a few test
calculations with a better method to check.

So, if we call HF, MP2 and CCSD ab initio, we can as well call minimal
basis, vdz and vtz ab initio. There is no systematic way to make B3LYP
(in the complete basis set limit) more accurate, and this is why DFT
isn't ab initio.

  Herbert

John McKelvey jmmckel:+:gmail.com wrote:
> Kirk,
>
> Your comment is correct with respect to construction of basis sets;
> however in any of the ZDO schemes, or other more elegant schemes, the
> choice of basis set, the choice of post-SCF treatment, or the choice of
> a DFT functional [or its construction] to get results that best
> reproduce experiment is routinely done and is either semi-empirical or
> purely empirical.  Which term suits the best, I do not know.  IMHO,
> "Everybody adjusts something to get the best answer."
>
> Regards,
>
> John McKelvey
>
> On Dec 12, 2007 6:59 PM, Kirk Peterson kipeters-*- wsu.edu
> <http://wsu.edu> <owner-chemistry],[ccl.net
> <mailto:owner-chemistry ],[ccl.net>> wrote:
>
>
>     Sent to CCL by: Kirk Peterson [kipeters-$-wsu.edu < http://wsu.edu>]
>
>     As a sidebar to this discussion, I have to strongly disagree that
>     basis set parameters, exponents or contraction coefficients,
>     use empirical data in their construction.  All commonly used basis
>     sets, even the Pople-style sets, are generated by optimizing
>     exponents and contraction coefficients to minimize (ab initio)
>     energies of atoms and sometimes molecules.  Some of the Pople-style
>     basis sets utilize scale factors to apply to atom-optimized exponents,
>     but these were based on (ab initio) molecular calculations
>     and not experimental data.
>
>     regards,
>
>     -Kirk
>
>     On Dec 12, 2007, at 8:21 AM, Rene Fournier renef+*+yorku.ca wrote:
>
>      >
>      > Sent to CCL by: Rene Fournier [renef\a/yorku.ca]
>      > David Craig and Robert Parr first used "ab initio" in quantum
>      > chemistry,
>      > see
>      > http://www.quantum-chemistry-history.com/Parr1.htm
>      > Near the middle of that page, Parr recounts:
>      >
>      > " Craig and I published this paper on "configuration interaction in
>      > benzene", where we took the pi-system and did essentially a complete
>      > configuration interaction calculation on it.
>      >
>      > That has some trivial historical interest in that it was there that
>      > the
>      > word, the term ab initio was introduced. Craig and Ross had computed
>      > everything from the start in London and I had personally computed
>      > everything from start in Pittsburgh. Then we compared our answers
>      > when we
>      > were finished- This involved computing of all the integrals as
>     best as
>      > they could be done and selecting the configurations to mix for the
>      > ground
>      > and exited states because there were electronic states that were of
>      > experimental interest and we checked our answers one against each
>      > other
>      > when we were finished. And what the paper says is, that these
>      > calculations
>      > were done ab initio by Craig and Ross and by me, independently. And
>      > Mulliken later said that this was the introduction of the term ab
>      > initio
>      > into quantum chemistry. In the short review that you have, I talk
>      > about
>      > this and reproduce a picture of a letter from Craig to me where he
>      > uses
>      > the term ab initio in a different context. So ab initio was
>      > introduced in
>      > the quantum chemistry by Craig in a letter to me and I put it
>     into the
>      > manuscript. That's where ab initio came from.  "
>      >
>      >
>      > Funny thing is Parr later became a champion of Density Functional
>      > Theory
>      > and for many years (70's, 80's) DFT practitioners were often
>      > criticized
>      > for doing calculations that were not "ab initio".  I think views have
>      > changed now;  "first-principles" was introduced probably to say
>      > "mostly
>      > not empirical" but without the implications "ab initio" had acquired
>      > over
>      > the years.  The term "ab initio calculation", as it's commonly used,
>      > very rarely refers to a calculation "devoid of empiricism", for
>      > example
>      > the choice of basis set parameters is almost always empirical,
>      > see discussion on
>      >
>     http://www.ccl.net/chemistry/resources/messages/2001/11/28.002-dir/index.html
>      >
>      >  Rene Fournier                   Office:  303 Petrie
>      >  Chemistry Dpt, York University  Phone: (416) 736 2100 Ext. 30687
>      >  4700 Keele Street,  Toronto     FAX:   (416)-736-5936
>      >  Ontario, CANADA   M3J 1P3       e-mail: renef*_* yorku.ca
>     <http://yorku.ca>
>      >
>      >
>      > On Wed, 12 Dec 2007, Christoph Etzlstorfer christoph.etzlstorfer .
>      > jku.at <http://jku.at > wrote:
>      >
>      >> There is a story about that in Michael J.S. Dewars biography "A
>      >> semiempirical life", American Chemical Society, 1992, p. 129.
>      >>
>      >> Best regards
>      >>
>      >> Christoph
>      >>
>      >>
>      >> Am 11.12.2007 um 03:13 schrieb Tommy Ohyun Kwon ohyun.kwon _
>      >> chemistry.gatech.edu <http://chemistry.gatech.edu>:
>      >>
>      >>>
>      >>> Sent to CCL by: Tommy Ohyun Kwon [ohyun.kwon .
>     chemistry.gatech.edu < http://chemistry.gatech.edu>]
>      >>> Dear CCLers;
>      >>> I would appreciate it if anyone could tell me who used the term of
>      >>> "ab initio
>      >>> calculations" first.
>      >>> Thank you very much for your kind attention.
>      >>>
>      >>> Best wishes,
>      >>>
>      >>> Tommy
>      >>>
>      >>>
>      >>> --
>      >>> Tommy Ohyun Kwon, Ph.D
>      >>> School of Chemistry and Biochemistry
>      >>> Georgia Institute of Technology
>      >>> Atlanta Georgia, 30332
>      >>> Email: ohyun.kwon]*[chemistry.gatech.edu
>     < http://chemistry.gatech.edu>
>      >>>
>      >>>
>      >>>
>      >>> -= This is automatically added to each message by the mailing
>      >>> script =-
>      >>> To recover the email address of the author of the message, please
>      >>> change> Conferences: http://server.ccl.net/chemistry/announcements/
>      >>> conferences/
>      >>>
>      >>> Search Messages: http://www.ccl.net/htdig  (login: ccl, Password:
>      >>> search)>
>      >>>
>      >>
>      >> ####################################################
>      >>                                   www.etzlstorfer.com
>     <http://www.etzlstorfer.com>
>      >> ***********************************************************
>      >> Dr. Christoph Etzlstorfer       Phone:  *43-732-2468-8750
>      >> Universitaet Linz              Fax:    *43-732-2468-8747
>      >> A-4040 Linz               E-mail: christoph.etzlstorfer,+,jku.at
>     < http://jku.at>
>      >> Austria                   http://www.orc.uni-linz.ac.at
>      >> ####################################################
>      >>
>      >>
>      >>
>      >>
>      >>
>      >
>      >
>      >
>      > -= This is automatically added to each message by the mailing script
>      > =-
>      > To recover the email address of the author of the message, please
>      > change> Conferences: http://server.ccl.net/chemistry/announcements/
>      > conferences/
>      >
>      > Search Messages: http://www.ccl.net/htdig  (login: ccl, Password:
>      > search)>
>      >
>
>
>
>
>
>
>
>
>     E-mail to subscribers: CHEMISTRY],[ccl.net
>     <mailto: CHEMISTRY],[ccl.net> or use:>
>     E-mail to administrators: CHEMISTRY-REQUEST],[ccl.net
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--
Herbert Fruchtl
EaStCHEM Fellow
School of Chemistry
University of St Andrews



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