Subject: Re: SUMMARY: The "birth-year" of computational chemistry? FOUND?!

From: Lingran Chen <[email-masked]>
Date: Fri, 17 Mar 2000 19:17:13 -0800

Dear CCLers:

I have received a lot of replies to my questions (for detail, see my
original email message shown below):

> 1. Who published the first paper about using an electronic
> computer to solve a(ny) chemical problem?
> 2. Who wrote the first quantum chemistry program?

Before giving the summary, I would like to clarify three points first:

(a) Some people asked 'What excactly do you mean by "computational
chemistry"?' (CC).
This is a good question.
There are many different versions of "definition" of CC. For example,
many chemists equate it with molecular mechanics. This can be regarded
as a "narrow definition" of CC.

On the other hand, many books with their titles containing CC cover both
molecular mechanics and computational quantum chemistry, such as Tim 
Clack’s famous book "A Handbook of CC" published in 1985 and Jensen’s
"Introduction of CC" published in 1998. This is a "medium definition".

The CC used in my email message refers to a "broad definition":
"CC is a sub-field of chemistry where the primary focus is on the
systematic development of computational methodologies and computer
systems, and application of them to solve any chemically-related
problems." 
Thus, this CC covers not only the two areas mentioned above, but also
cheminformatics and many others. A good book which meets this definition
is the prestigious "Encyclopedia of Computational Chemistry" published
in 1998.

(b) Another point I want to clarify is that by "an electronic computer" 
I mean those "similar" to the "first generation of computers", 
but not "hand-cranked calculating machines"/"mechanical computers".
Thus, the earliest such electronic computers are, for example,
 
1943: First electronic computer (Colossus ) built in Britain. 

1943: A more general purpose electro-mechanical programmable computer
(Harvard Mark I) built at Harvard University with backing from IBM.

1946: The first general-purpose computer, ENIAC (Electronic Numerical
Integrator and Computer), was invented. 

(c) About the "birth-year" of CC: 
It's quite difficult to determine the starting point of an area. For
example, what's the birth-year of the computer? 
The following web site (I mentioned before) 
	http://ox.compsoc.net/~swhite/timeline.html
lists "500 B.C." as the starting point of "A Brief History of Computing"!
However, it should be quite acceptable to treat either 1943 or 1946 as
the birth-year of the "modern" electronic computer. And then we can further
say that but its "origins" date back much earlier.

Similarly, we may treat the publication year of the paper describing
the first use of a "modern" electronic computer in chemistry as the
"modern" CC, and then mention that CC's "origins" date back much earlier.
Thus, it becomes possible and reasonable to determing the "birth-year" of CC.

The earliest paper meeting the above requirements found so far
was published in _1946_:

G. W. King, P. C. Cross and G. B. Thomas,  J. Chem. Phys. 14 35 1946.

This paper describes the calculation of line strengths and positions 
in the rotational spectra of asymmetric rotors.  The authors are
well-respected spectroscopists. An interesting excerpt is:

"In the International Business Machines all the quantities used in the
calculations are supplied on cards, their numbers or identification
letters appearing as holes punched in certain locations.  The machines
read the information by brushes which make electrical contacts through
the holes as the cards run through the machine."

The article goes on to describe the key punch, sorter, collator, reproducer,
multiplier and summary tabulator.

This paper was found by Prof. Roy Edward Bruns <[email-masked]>.
Thank you again, Prof. Bruns!

Richard Gillilan <[email-masked]> mentioned:

>I seem to recall, that Monte Carlo methods invented during the 
>Atom Bomb project in the 40's may have been the first electronic 
>computer calculations on condensed matter, although they may not qualify as
>chemistry. 

All the replies are listed below in the order I received them.
Thank you very much for your replies!
-Lingran

--------------------Beginning of Lingran's original questions: ------------
Lingran Chen wrote:
> 
> Dear CCLers:
> 
> In the Encyclopedia of Computational Chemistry (ECC), there are some
> interesting
> statements about the "birth-year" of computational chemistry. For
> example,
> 
> 1. "Computational chemistry has existed for half a centrury, ..."
>    - Forword of ECC by Prof. Pople (1997).
> 
> Thus, the birth-year of CC is about 1947.
> 
> 2. "Although its origins date back much earlier,
>    Computational Chemistry evolved into a distinctly discernible
> discipline
>    three decades ago ..."
>    - Preface of ECC by Prof. Schleyer (1997?)
> 
> Thus, the birth-year of CC is about 1967.
> 
> 3. "The general availability of computers at major research laboratories
> and
>    the availability of FORTRAN as a general programming language to make
> use of
>    these computers marks
>    1960 as approximately the beginning of modern computational chemistry
> >..."
>    - "HISTORY OF COMPUTATIONAL CHEMISTRY: A PERSONAL VIEW"
>    by prof. Streitwieser. (ECC, p.1238)
> 
> Here, the birth-year of CC is 1960.
> 
> I have two questions:
> 
> 1. Who published the first paper about using an electronic
> computer to solve a(ny) chemical problem?
> 
> In my personal record, the earlest publication is:
> 
> P D. Zemany, "Punched Card Catalog of Mass Spectra Useful in Qualitative
> Analysis,"
> Anal. Chem., 22, 1950, 920.
> 
> 2. Who wrote the first quantum chemistry program?
> 
> The answers to the above questions may indicate the "reasonable"
> birth-year of CC.
> Thanks in advance.
> 
> -Lingran
> 
> ***********************************
> Lingran Chen, Ph.D.
> Advisory Scientist
> MDL Information Systems, Inc.
> 14600 Catalina Street
> San Leandro
> CA 94577
> U.S.A.
> 
> Phone: (510) 895-1313
> FAX:   (510) 614-3616
> 
> Email: [email-masked]
> Web:   http://www.mdli.com
> ***********************************
-------------------- End of Lingran's original questions ------------

Subject: "Birth year" of CC
Date: Wed, 23 Feb 2000 10:20:30 +0200 (IST)
From: Harold Basch <[email-masked]>
To: [email-masked]

Sir:

I recommend that you see, NBS Technical Note 438, issued December 1967,
"Compendium of Ab Initio Calculations of Molecular Energies and Properties"
by Morris Krauss. This ~140 page report describes calculations on hundreds
of molecules (mostly diatomics) with references going back to the 1950s.
MK can be reached at Email, [email-masked]. He is one of the
best references for answering your question.

Harold Basch
Department of Chemistry
Bar Ilan University
Ramat Gan 52900
Israel
Phone: (972)-3-5318311
FAX:   (972)-3-5351250
Email: [email-masked]
---------------
Subject: CCL:The "birth-year" of computational chemistry?
Date: Wed, 23 Feb 2000 09:52:31 +0100
From: Christoph van Wuellen <[email-masked]>
To: Lingran Chen <[email-masked]>
CC: [email-masked]
            1

I have no reference at hand, but I think computers were used even before
in the field of X-Ray structure analysis.
-- 
---------------------------+------------------------------------------------
Christoph van Wullen       | Fon (University):  +49 234 32 26485
Theoretical Chemistry      | Fax (University):  +49 234 32 14109
Ruhr-Universitaet          | Fon/Fax (private): +49 234 33 22 75
D-44780 Bochum, Germany    | eMail:
[email-masked]
---------------------------+------------------------------------------------

Subject: Re: CCL:The "birth-year" of computational chemistry?
Date: Wed, 23 Feb 2000 19:17:05 +0930
From: Brian Salter-Duke <[email-masked]>
To: Lingran Chen <[email-masked]>

I believe it is correct that that the first correct ab initio calculation on a
molecule was carried by students of Frank Boys in about 1957/58 on CH2O.
This used Gaussian orbitals. By correct, I mean just that - something that can
be essentially reproduced using say Gaussian. It was run on a Ferranti Pegasus
machine using 5 hole paper tape to store the integral list at each step of the
SCF. The paper tape from the punch was I gather fed straight into the paper
tape reader with a whole mess of tape all over the floor while the job ran all
night.

Of course there were ab initio calculations on diatomic molecules using
Slater orbitals earlier. The work of Ransil springs to mind here.

The question posed depends on what we mean by "computational". Does
cranking the old hand machines count? In which case we are back to
Heitler-London in 1927. 

Regards, Brian Duke.

-- 
        Associate Professor Brian Salter-Duke (Brian Duke)
Chemistry, Faculty of Science, IT and Education, Northern Territory
University,
          Darwin, NT 0909, Australia.  Phone (61) (0)8-89466702
e-mail: [email-masked]  or [email-masked]
----------------
Subject: Re: CCL:The "birth-year" of computational chemistry?
Date: Wed, 23 Feb 2000 10:10:37 +0000
From: Huub van Dam <[email-masked]>
Organization: CCLRC Daresbury Laboratory
To: Lingran Chen <[email-masked]>

Hi Lingran,

I don't have the reference at hand so at the risc of saying something stupid I
think I remember that it was S.F. Boys who suggested the use of gaussian basis
functions in ab initio calculations in 1950 (Proc. Roy. Soc. London?).
The reason was that the optimal Slater functions being of an exponential form
led to unsurmountable problems in calculating 2-electron intergrals for multi
atomic systems (multi being 3, 4, or more).

So 1950 is a sure upper limit for a birth year. Perhaps if you find the paper I
mentioned you get close to finding the actual answer from the references. But
then again I think there was Hylleraas who performed the first calculation on
the Helium atom using a wavefunction that had terms including the 
inter-electronic distance explicitly. This is still thought of as a rather
accurate calculation, and although I can't remember the reference the year
1928 comes to mind. However I don't think he used an electronic computer,
human computers were more common in those days.

Huub

========================================================================

Huub van Dam                               E-mail: [email-masked]
CCLRC Daresbury Laboratory                  phone: +44-1925-603362
Daresbury, Warrington                         fax: +44-1925-603634
Cheshire, UK
WA4 4AD

========================================================================

Subject: CCL:The "birth-year" of computational chemistry?
Date: Wed, 23 Feb 2000 12:17:47 +0100
From: Jens Spanget-Larsen <[email-masked]>
Organization: Roskilde Universitetscenter
To: Lingran Chen <[email-masked]>

Dear Lingran Chen:

> In the Encyclopedia of Computational Chemistry (ECC), there are some 
> interesting statements about the "birth-year" of computational chemistry.
> For example,  .......

I think your question should probably be formulated more precisely. What 
excactly do you mean by "computational chemistry"?  Do you mean theoretical 
chemical investigations based on the use of electronic computers? What about 
mechanical computers?  And what about computations performed with 'pencil and 
paper'?

Yours, Jens >--<
                             
=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=
JENS SPANGET-LARSEN         Phone:  +45 4674 2000  (RUC)
Department of Chemistry             +45 4674 2710  (direct)
Roskilde University (RUC)   Fax:    +45 4674 3011 
P.O.Box 260                 E-Mail: [email-masked]
DK-4000 Roskilde, Denmark   http://www.rub.ruc.dk/dis/chem/psos/
=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=

Subject: CCL:The "birth-year" of computational chemistry?
Date: Wed, 23 Feb 2000 07:54:12 -0500
From: Richard Gillilan <[email-masked]>
To: [email-masked]

> I have two questions:
> 
> 1. Who published the first paper about using an electronic
> computer to solve a(ny) chemical problem?

I seem to recall, that Monte Carlo methods invented during the 
Atom Bomb project in the 40's may have been the first electronic 
computer calculations on condensed matter, although they may not qualify as
chemistry. I remember a facinating talk by W. Wood (Los Alamos) at a computer
simulation conference at University of Utah about 10 years ago entitled
"The Early History of Computer Simulations". I'll try to dig up his paper.

Richard Gillilan
Cornell Theory Center
----------------

Subject: CCL:The "birth-year" of computational chemistry?
Date: Wed, 23 Feb 2000 09:57:52 -0500
From: Frank Marchese <[email-masked]>
To: [email-masked]

What do you mean by "electronic" ? Are the computer's analog or 
digital? Lord Kelvin invented/ used an analog computer called
the "differential analyzer" to solve 2nd order differntial equations,
in particular for analysis of tides. In the late 1920s, Vannevar
Bush of MIT re-invented Kelvin's analog machine on a grander scale.
Douglas Hartree spent time with Bush, took the basic plans back to
England and built his own. During the 1930s, Bush's, Hartree's, and 
similar machines built in physics departments were used to solve the
Schrodinger equation. 

The best history on this stuff remains Herman Goldstone's book: 
The Computer from Pascal to von Neumann (Princeton U. Press)

See the references within.

Francis T. Marchese
Professor
Dept. of Computer Science
Pace University
-------------------

Subject: CCL:The "birth-year" of computational chemistry?
Date: Wed, 23 Feb 2000 09:58:03 -0500 (EST)
From: M Dominic Ryan <[email-masked]>
To: [email-masked]

I dug into this question about 12 years ago.  It depends of course on just
what you call computational chemistry.  Does it have to be using a
computer?  I would argue that should not be a requirement.  Rather the
real underlying field is the construction of a numeric simulation that
represents 'reality' in a context that permits testing concepts and
thereby learning something.  Today we use computers in their current form,
perhaps this will change in the decades to come.

I point back to early spectroscopic work.  The earliest I think is work by
Andrews, in the 20s.  Once citation I have is in Physical Reviews, v36,
p531, 1930, Kettering, Shutts and Andrews (General Motors Corporation).
"A representation of the Dynamic Properties of Molecules by Mechanical
Models".  I think of this as the birth of molecular modeling.  They built
molecular models of things like toluene, benzene, chlorobenzene using
steel balls and calibrated springs.  They attached an oscillator and swept
the frequency.  They then used a strobe light an found the standing
waves.  In this way they mapped out a molecular mechanics model the IR and
Raman spectra.  They were then able to draw conclusions about the correct
molecular structure by doing the experiment on various bonding models of
benzene by having springs attached in different arrangements.  I think
they got it wrong in the end, but that sure looks like molecular mechanics
with an analog computer to me.

There is also the work by Urey and Bradley, whose names are still attached
to a force field, that begins around 1931 with a paper in Physical Review,
p1969, 1931 (apparently Bradley's Ph.D. thesis).  He discusses Andrew's
papers and also a paper I never saw by Bjerrum in physik. Ges. Ber. v16,
p737, 1914, proposing those sorts of forces acting upon bonded atoms He
of course also cites Slater (1931) and Pauling JACS,v53,p1367, 1931, as
discussing the nature of the forces on a chemical bond.

Still later, I put Frank Westheimer (with John Mayer) at the birth of
computational chemistry using numerical methods.  He calculated an
activation energy for racemization of 2,2'-dibromo-4,4'-dicarboxydiphenyl
in J. Chemical Physics, v15, p252, 1947 (there is also an earlier paper
v14, p733,1946).  He used an exponential function to describe the rates
and pull out constants.

Other names at that time are T.L. Hill, J. Chem. Phys. v14,465 (1946)
and W. Gordy, J.Chem.Phys 14,305(1946).
__
M. Dominic Ryan   (610)-270-6529     SmithKline Beecham Pharmaceuticals 
Internet:  [email-masked]     King of Prussia, PA  
----------------------

Subject: Re: CCL:The "birth-year" of computational chemistry?
Date: Wed, 23 Feb 2000 10:16:10 -0800
From: wsteinmetz <[email-masked]>
Organization: Pomona College
To: Lingran Chen <[email-masked]>

The landmark CALCULATION is the study of James and Coolidge [H. M. James
and A. S.Coolidge, J. Chem. Phys., Volume 1, p. 825 (1933)] in which they
used the new quantum mechanics to calculate the bond length and bond
dissociation energy of diatomic hydrogen to EXPERIMENTAL
accuracy.  The existence of diatomic hydrogen, a result derived from the
application of Avogadro's principle, was a scandal in the nineteenth century.
Its existence was firmly rejected by most scientists and
the contraversy delayed the development of chemistry.  Avogadro's
hypothesis was revisited by Canizarro at the famous meeting in Karlsruhe.

The existence of diatomic hydrogen is radically inconsistent with
classical physics and the explanation of its bonding was one of the triumphs
of quantum mechanics.  In particular, the crucial calculation of
James and Coolidge established that it was not simply a qualitative
model but was ab initio. So, in a sense, all serious work in computational
molecular quantum mechanics can be traced to James and Coolidge who therefore
deserve the credit as the fathers of serious molecular modelling.
--------------------

Subject: Re: CCL:The "birth-year" of computational chemistry?
Date: Wed, 23 Feb 2000 15:58:54 -0300
From: Roy Edward Bruns <[email-masked]>
To: Lingran Chen <[email-masked]>

Dear Dr. Chen,
     The earliest reference I found for the use of computers in chemistry is:
G. W. King, P. C. Cross and G. B. Thomas,  J. Chem. Phys. 14 35 1946.
This fact suggested the theme of our  1995 Brazilian Theoretical Chemistry
Symposium " Theoretical Chemistry: A Half Century of Computation."
Has anyone found an earlier reference?

Sincerely,
Roy E. Bruns
Professor of Chemistry
--------------------

Subject: 
Date: Wed, 23 Feb 2000 14:12:53 -0500 (EST)
From: Rene Fournier <[email-masked]>
To: [email-masked]

Dear Dr Chen,

I'm sure you will get many different answers to the questions
- Who wrote the first quantum chemistry program? 
and
-When was "computational chemistry" (CC) born?

   I guess there was a gradual evolution and unless we agree
on strict definitions of "quantum chemistry", "computer", "program",
etc... there is no definite answer.  Rather than a birth-date of
CC, it's more appropriate maybe to talk about a series of landmark
papers.  One of these was

H.O. Pritchard and F.H. Sumner,
"Application of electronic digital computers to molecular orbital
problems. I. The calculation of bond lengths in aromatic hydrocarbons".
Proc. Roy. Soc. London, vol A226, 128-140 (1954).

It's apparently the first MO theory calculation using an electronic
digital computer.  It's remarkable how "modern" this paper is.  Despite
very limited computing means, it reports computed properties of
"large" molecules (up to 30 C atoms) --- the kind of things that
interests not only theoriticians but also bench chemists.

Pritchard and Sumner went on to produce a series of papers that are
are quite modern in spirit, e.g., 

J. Chem. Soc. 1041 (1955) "steric hindrance in aromatic hydrocarbon
systems" combines MO energies and force-field;

Proc. Roy. Soc. London A235 (1956) 136-143 "The application of electronic
digital computers to molecular orbital problems. II A new approximation
for hetero-atom systems"  recognizes the connection between electronegativity
and derivative of orbital energy w.r.t. occupation number, which is an
important idea in modern density functional theory. 

Cheers,
        Rene Fournier.
 --------------------------------------------------------------------
 | Rene Fournier                  | Bureau/Office  303 Petrie       |
 | Chemistry Dpt, York University |      (416) 736 2100 Ext. 30687  |
 | 4700 Keele Street,  Toronto    | FAX: (416-736-5936)             |
 | Ontario, CANADA   M3J 1P3      | e-mail: [email-masked]          |
 --------------------------------------------------------------------
 |                http://www.chem.yorku.ca/profs/renef/             |
 --------------------------------------------------------------------

Subject: Re: CCL:The "birth-year" of computational chemistry?
Date: Thu, 24 Feb 2000 08:34:11 +0930
From: Brian Salter-Duke <[email-masked]>
To: Lingran Chen <[email-masked]>

On Wed, Feb 23, 2000 at 09:45:20AM -0800, Lingran Chen wrote:
> Brian Salter-Duke wrote:
>> 
>> I believe it is correct that that the first correct ab initio calculation on a
>> molecule was carried by students of Frank Boys in about 1957/58 on CH2O. This used
>> Gaussian orbitals. By correct, I mean just that - something that can be essentially
>> reproduced using say Gaussian. It was run on a Ferranti Pegasus machine using 5 hole
>> paper tape to store the integral list at each step of the SCF. The paper tape from
>> the punch was I gather fed straight into the paper tape reader with a whole mess of
>> tape all over the floor while the job ran all night.
>> 
>> Of course there were ab initio calculations on diatomic molecules using Slater orbitals
>> earlier. The work of Ransil springs to mind here.
> 
> Interesting message. Do you have any references?

The Ransil paper is I think in 1956. It is discussed in detail with the 
reference in "Atoms and Molecules" by Karplus and Porter.

The Boys stuff was I think in Phys Rev but it could have been J Chem Phys. 
The other authors were Fletcher and perhaps Reeves. How do I know how they 
did it? Sorry, no references. I have been around a long time. I started in 
1960 and I was in England for a long time. It is the sort of thing you talk 
about at conferences over a few beers.

Cheers, Brian.
 
>> The question posed depends on what we mean by "computational". Does cranking the old
>> hand machines count? In which case we are back to Heitler-London in 1927.
> 
> I personally more like "computer chemistry".
> Thanks.
> -Lingran
> 

>> --
>>         Associate Professor Brian Salter-Duke (Brian Duke)
>> Chemistry, Faculty of Science, IT and Education, Northern Territory University,
>>           Darwin, NT 0909, Australia.  Phone (61) (0)8-89466702
>> e-mail: [email-masked]  or [email-masked]

----------------------
Subject: Re: CCL:The "birth-year" of computational chemistry?
Date: Wed, 23 Feb 2000 18:54:42 -0500 (EST)
From: "stanley a. hagstrom" <[email-masked]>
To: Lingran Chen <[email-masked]>

Another interesting question.  I have one of my own.  Do you distinguish
between quantum chemistry and computational chemistry?  If one doesn't
during the early years then sometime between 1950 and 1955 would be a 
reasonable starting date.  I was around and involved then and I know we
thought we were doing something new and different.  Even if we didn't
have the largest machines.  One way to get a handle on this would be to
determine when most of the basic computational algorithm were formulated
and proven to be viable.  A great deal of work was done prior to Fortran.

Computational chemistry is an extremely loose term not much to my liking.
But I'm an old hand who describes himself as a quantum chemist, whose
research is perhaps not very "chemical" in the view of many chemists.

Keep up the questions.  Especially the historical ones.  It takes me
back to the "good old days".

Stan Hagstrom
-------------------

Subject: CCL:The "birth-year" of computational chemistry?
Date:  Wed, 23 Feb 2000 21:16:06 -0500 (EST)
From: Peter Shenkin <[email-masked]>
To: [email-masked]

Hi, Dominic,

When I was in high-school, I built a suspended ball-spring
version of the Kettering device as a sort of senior project.  
This brings back memories.

But I don't think you'd call this computational chemistry. :-)
I think that term should be reserved for the use of digital
computers.  In this regard, I believe the Metropolis paper
was in 1948, and might have been the first.

        -P.

On Wed, 23 Feb 2000, M Dominic Ryan wrote:
> I point back to early spectroscopic work.  The earliest I think is work by
> Andrews, in the 20s.  Once citation I have is in Physical Reviews, v36,
> p531, 1930, Kettering, Shutts and Andrews (General Motors Corporation).
> "A representation of the Dynamic Properties of Molecules by Mechanical
> Models".  I think of this as the birth of molecular modeling.  They built
> molecular models of things like toluene, benzene, chlorobenzene using
> steel balls and calibrated springs.  

--
** Whether the playing field is level depends on the coordinate system. ***
********* Peter S. Shenkin; Schrodinger, Inc.; (201)433-2014 x111 *********
*********** [email-masked]; http://www.schrodinger.com ***********
----------------

Subject: Re: CCL:The "birth-year" of computational chemistry?
Date: Thu, 24 Feb 2000 13:00:15 -0300
From: Roy Edward Bruns <[email-masked]>
To: Lingran Chen <[email-masked]>

Dear Dr. Chen,
    The article I referred to describes the calculation of line strengths and
positions in the rotational spectra of asymmetric rotors.  The authors are
well-respected spectroscopists.  You might be interested in reading the 
section of the paper dealing with the calculations. An interesting excerpt is:

" In the International Business Machines all the quantities used in the
calculations are supplied on cards, their numbers or identification letters
appearing as holes punched in certain locations.  The machines read the
information by brushes which make electrical contacts through the holes as
the cards run through the machine."

The article goes on to describe the key punch, sorter, collator, reproducer,
multiplier and summary tabulator.

Sincerely,
Roy Bruns

Lingran Chen wrote:

> Dear Prof. Bruns:
> Thank you very much for your message.
> What's the subject of the paper
> "J. Chem. Phys. 14 35 1946"?

----------------------------------
Subject: CCL:estimate FP operations in Comp Chem
Date:  Fri, 25 Feb 2000 09:52:10 -0500
From:  Steve Williams <[email-masked]>
To: [email-masked]

I'd like to invite the CCL community to help me make an estimate, somewhat
related to the "birth of computational chemistry" thread recently on CCL.

How many moles of floating point operations have been devoted to computational
chemistry? As an example, a 1 teraflop machine, running for 5 years, nonstop,
will have done something on the order of 1E20 floating point operations, or
about 1/6000 of a mole.  

Since teraflop machines are new (all much younger than 5 years), and
certainly not devoted exclusively to computational chemistry, I suspect
that in the entire history of computational chemistry we have not (total in
the world) quite used a mole of operations.

I invite anyone who wishes to make their own estimates of total global
comp. chem. FP operations, and I'll summarize.  I am giving a talk next
month and thought this might be an amusing statistic to use.

Thanks,
Steve

*****************************************
Steve Williams               F    F    F
Chemistry                     \  / \  /
Appalachian State University   Al   Al
Boone, NC 28608               /  \ /  \
USA                          F    F    F
[email-masked]
828-262-2965
<http://www.acs.appstate.edu/~willsd>

-----------------------
Subject: CCL:The "birth-year" of computational chemistry?
Date: Mon, 28 Feb 2000 00:42:07 -0600
From: Ernest Chamot <[email-masked]>
To: Computational Chemistry List <[email-masked]>

This discussion has been interesting because, as Dominic Ryan pointed out:

>. . . .  It depends of course on just 
>what you call computational chemistry.

Use of the term to mean: the ability to describe a chemical or chemical
process mathematically (Theoretical Chemistry?  Pople's & Ryan's point
of view?), vs. actually carrying out the necessary computation
(Calculational Chemistry?)  The use of computers by chemists (analyzing
data, etc.; Computers in Chemistry?) vs. modeling a chemical or chemical
process with the computer (Molecular Modeling?).  Use of "Computer" in
the original, more general sense (a machine that returns a numerical
result; Marchesa's point of view?), vs. a more modern meaning
(understood to refer to electronic, digital computers?)  Etc.

IMHO, what makes Computational Chemistry distinct, is that our chemical
theories have been implemented in software, and computer hardware has
developed that can run that software, to the point that it is practical
to routinely APPLY theory to accurately model molecular structure and
chemical processes, and to calculate numerical results which were
previously only available experimentally.  So from that point of view,
the "Birth" of Computational Chemistry must be when these theories
started_ being converted into software and run on the type of computer
hardware that _ultimately_ became fast enough to _routinely_ model
chemistry.  So I think Lingran's second question comes close to defining
the birth:  

>2. Who wrote the first quantum chemistry program?

The only thing I would add, is that since only electronic, digital
computers have been developed to be programmable and fast enough to
routinely do these calculations, I would say the birth year is the year
that someone first coded and ran a quantum chemistry (or other molecular
modeling) program on an electronic, digital computer.  The worlds first
electronic, digital computer, ENIAC (Electronic Numeric Integrating
Automatic Computer), was constructed at the University of Pennsylvania
in 1945, this sets an early limit for the birth of Computational
Chemistry.

With this point of view in mind, I have some inside information (albeit
second-hand) about the early days, that is relevant.  I have a close
relationship with one of the programming pioneers at Argonne National
Laboratories.  Cynthia Chamot (yes, this is my Mother, and I'm quite
proud of her) was one of the early programmers hired by Argonne to
program the third, all electronic, digital computer ever built, AVIDAC.
AVIDAC (Argonne's Version of the Institute's Digital Automatic Computer)
was constructed around 1950, only 5 years after ENIAC.  (Argonne's
second computer, by the way, was named "George.")

She recalls working as part of a team with  several others (including
Ruth Freshour & Gerry Duffy) in the Applied Math Division, to develop
code for John Weil in the Chemistry Division, by 1956.  She specifically
remembers the need for part of the code to find eigenvalues and invert
13x13 matrices with only 512 "words" (not K) of memory to work in!  She
isn't sure whether this was a QM calculation, but it looks like
Computational Chemistry had started at Argonne sometime between 1950 and
1956.

Prior to that, the military used computers on the Atomic Bomb project,
as  Richard Gillian mentioned:

>I seem to recall, that Monte Carlo methods invented during the 
>Atom Bomb project in the 40's may have been the first electronic 
>computer calculations on condensed matter, although they may not qualify as
>chemistry. I remember a facinating talk by W. Wood (Los Alamos) at a computer

I know one of the earliest uses was to analyze the probability of one
nuclear reaction triggering multiple nuclear reactions, to determine
exactly what constituted a critical mass.  Is this the 'Monte Carlo"
calculation referred to in Gillian's reference?  If so, I would consider
this a Computational Physics or statistical computation rather than
Computational Chemistry.  If it really is a Chemistry code, then the
birth of Computational Chemistry may be before 1950: as early as 1945.

EC
---

Ernest Chamot
Chamot Laboratories, Inc.
530 E. Hillside Rd.
Naperville, Illinois 60540
(630)637-1559
[email-masked]
http://www.chamotlabs.com/cl

----------------------
Subject: CCL:The "birth-year" of computational chemistry?
Date: Mon, 28 Feb 2000 09:40:13 +0000
From: Joerg Grunenberg <[email-masked]>
To: Ernest Chamot <[email-masked]>, [email-masked]

Ernest Chamot wrote:

>
> The worlds first electronic, digital computer, ENIAC (Electronic Numeric
> Integrating Automatic Computer), was constructed at the University of
> Pennsylvania in 1945, this sets an early limit for the birth of
> Computational Chemistry.
>

Dear Ernest Chamot

maybe the ENIAC was the first computer in the world.

The first computer in europe, Z3 (Zuse 3) was finished by Konrad Zuse in
1941 (Berlin, Germany).

J. G.

--
Joerg Grunenberg, Org. Chemie, Hagenring 30, 38106 Braunschweig
email: [email-masked] phone: +49 531 391 5252
URL: http://www.tu-bs.de/institute/org-chem/grunenberg/grunenberg.html

--------------------
Subject: CCL:The "birth-year" of computational chemistry?
Date: Mon, 28 Feb 2000 12:05:50 +0100 (MET)
From: Harald Svedung <[email-masked]>
To: Ernest Chamot <[email-masked]>
CC: Computational Chemistry List <[email-masked]>

Hi all!

Ernest Chamot writes about some trial definitions on some cc-related  Terms.

Maby it's a little unfortunate that the term Molecular Modeling has 
become limited to the use of computers as the term says nothing about 
using any means of numerical descriptions what so ever. Yes, numerical 
meassures are practical to use, and digital, even electronic, computers 
are what we often think of in terms of tools, but the spring-and-ball 
contraption is, allthough a rugh and classical one, a modell of a 
molecular system and to handel it is therefore to do Molecular  Modeling.

There is of course Computational Molecular Modeling with the 
'Computational' being implicit.

;-)
/Harald

Harald Svedung (Ph.Lic.)                phone:          +46-31-7722816
Department of Chemistry                 fax:            +46-31-167194
Physical Chemistry                      home phone:     +46-31-240897,
+46-709223206    
Goeteborg University                    home e-mail:   
[email-masked]
SE-412 96 Goeteborg, Sweden             www.che.chalmers.se/~svedung/   
--------------------

Subject: CCL:The "birth-year" of computational chemistry?
Date: Mon, 28 Feb 2000 14:15:42 +0000
From: "Rzepa, Henry" <[email-masked]>
To: [email-masked]

>.. The worlds first electronic, digital computer, ENIAC (Electronic Numeric
> Integrating Automatic Computer), was constructed at the University of
> Pennsylvania in 1945, this sets an early limit for the birth of
> Computational Chemistry.

A rather US centric claim.  There was certainly a computer built by
Turing well before  1945 at Bletchley park, to decode the  German  Enigma
ciphers which probably qualifies. Turing was also associated with Manchester
University, that I believe also has a prior claim  to
ENIAC.  No doubt reference to the textbooks (mine are at home and  I
write this from work) will clarify this issue.

Apologies for being slightly off topic!
-- 

Henry Rzepa. +44 (0)20 7594 5774 (Office) +44 (0)20 7594 5804 (Fax)
Dept. Chemistry, Imperial College, London, SW7  2AY, UK. 
http://www.ch.ic.ac.uk/rzepa/
---------------

Subject: CCL:The "birth-year" of computational chemistry?
Date: Mon, 28 Feb 2000 11:10:56 -0500
From: "David E. Bernholdt" <[email-masked]>
To: [email-masked]
CC: [email-masked]

I don't want to enter this fray except to say that one must be careful
to distinguish betweeen (a) analog and digital computers, and (b)
purpose-specific and general programmable computers.  Many early
computers were hardwired for specific tasks. I think you're free to
argue as much about the definition of the earliest computer as you are
about what constituted computational chemistry :-)

Incidentally, I know that Iowa State U claims that that the
Atanasoff-Berry Computer (built 1937-1942) was the first _digital_
computer, predating ENIAC. (http://www.scl.ameslab.gov/ABC/ABC.html)

--
David E. Bernholdt                      | Email:  [email-masked]
Northeast Parallel Architectures Center | Phone:  +1 315 443 3857
111 College Place, Syracuse University  | Fax:    +1 315 443 1973
Syracuse, NY 13244-4100                 | URL:   
http://www.npac.syr.edu

----------------------
Subject: CCL:The "birth-year" of computational chemistry?
Date: Mon, 28 Feb 2000 17:05:35 +0000
From: Tom Hawkins <[email-masked]>
To: [email-masked]

David E. Bernholdt [[email-masked]] said:

>I don't want to enter this fray except to say that one must be careful
>to distinguish betweeen (a) analog and digital computers, and (b)
>purpose-specific and general programmable computers.  Many early
>computers were hardwired for specific tasks. 

Manchester celebrated the 50th anniversary of the first digital stored
program computer (the 'Baby') in 1998:

http://www.computer50.org/

Among the celebrations was a competition to write a program for the first
machine - see details on http://www.cs.man.ac.uk/prog98/ where John Sargeant
(ex- competition coordinator) says:

"In my view, "stored-program computer" (i.e. "computer-with-software") is a
tautology, given the modern usage of the word "computer". It's difficult to
imagine running a competition like this for any of the "computers" which 
existed before the Baby. And we've seen that the store was (just) big enough
to make interesting programs possible. So if anybody else claims to have The
World's First Computer, ask them for details of their programming competition."

Dr Tom Hawkins             Osmetech plc
Sensor Technologist        Electra House, Electra Way, Crewe CW1 6WZ
[email-masked]   Tel +44(0)1270 216444 Fax +44(0)1270 216030 

--------------------
Subject: Re: CCL:The "birth-year" of computational chemistry?
Date: Mon, 28 Feb 2000 09:08:26 -0800
From: Lingran Chen <[email-masked]>
Organization: MDL Information Systems, Inc.
To: [email-masked]

If you are interested in the History of Computer, 
you may check the following web site.

http://ox.compsoc.net/~swhite/timeline.html

However, please be warned that some dates may not be absolutely correct!
-Lingran

David E. Bernholdt wrote:
> 
> I don't want to enter this fray except to say that one must be careful
> to distinguish betweeen (a) analog and digital computers, and (b)
> purpose-specific and general programmable computers.  Many early
> computers were hardwired for specific tasks. I think you're free to
> argue as much about the definition of the earliest computer as you are
> about what constituted computational chemistry :-)
> 
> Incidentally, I know that Iowa State U claims that that the
> Atanasoff-Berry Computer (built 1937-1942) was the first _digital_
> computer, predating ENIAC. (http://www.scl.ameslab.gov/ABC/ABC.html)
> 
> --
> David E. Bernholdt                      | Email:  [email-masked]
> Northeast Parallel Architectures Center | Phone:  +1 315 443 3857
> 111 College Place, Syracuse University  | Fax:    +1 315 443 1973
> Syracuse, NY 13244-4100                 | URL:    http://www.npac.syr.edu

-----------------------
Subject: CCL:The "birth year" of computational chemistry
Date: Mon, 28 Feb 2000 12:01:27 -0600 (CST)
From: TJ ODonnell <[email-masked]>
To: [email-masked]
CC: [email-masked]

Perhaps we should distinguish between analog, digital and human
computers, as well.  Some of the first applications of
quantum theory to chemisty (to molecules as opposed to atoms)
were carried out by Mulliken.  I'm not sure if I have it right,
but the story goes that Mulliken's father (a mathematician?)
actually performed the computations using pencil and paper.

And it's certainly true that people have been thinking of
computational chemistry for a long time.  Here are two favorite
quotes of mine from the 19th century.

"We are perhaps not far removed from the time when we shall be able
to submit the bulk of chemical phenomena to calculation." 
- Joseph Louis Gay-Lussac, Memoires de la Societe d'Arcueil 2:207 (1808)

"All of chemistry, and with it crystallography, would become a branch
of mathematical analysis which, like astronomy,
taking its constants from observation, would enable us to predict
the character of any new compound and possibly
the source from which its formation might be anticipated." 
- Charles Babbage, 1838, quoted in Faster than Thought,
B. V. Bowden, ed., Sir Isaac Pitman & Sons, Ltd., London, 1953, p. 12.

Two more quotes are at:
http://www.eecs.uic.edu/~tj/quotes.html#computational_chemistry

TJ O'Donnell
[email-masked]

------------------------
Subject: CCL:The "birth-year" of computational chemistry?
Date: Mon, 28 Feb 2000 16:26:08 -0500
From: "Luke A. Burke" <[email-masked]>
To: Ernest Chamot <[email-masked]>, [email-masked]

Ernest Chamot wrote:
> 
> This discussion has been interesting because, as Dominic Ryan pointed out:
> 
> >. . . .  It depends of course on just
> >what you call computational chemistry.
> 
> Use of the term to mean: the ability to describe a chemical or chemical
> process mathematically (Theoretical Chemistry?  Pople's & Ryan's point of
> view?), vs. actually carrying out the necessary computation (Calculational 
>...

Yes, very much so, but I think there was a definite point at which
Quantum Chemistry broke off from Quantum Mechanics. Almost all of us
quantum chemists start our calculations with not just RHF or UHF but the
LCAO-MO method. This is in the domain of linear algebra whereas much of
what went before was  differential equations. Linear algebra solutions
are the stuff of computer calculations and they were just right for the
vacuum tube computers as they are now for chips. These linear
combinations were probably what Ernest Chamot's mother was programming.
The two people who, independently, are responsible for the LCAO-MO
method being put on a firm theoretical foundation are C.C.J.Roothaan
(Rev.Mod.Phys.23,69,1951), G.G.Hall (Proc. Roy. Soc. A205, 541, 1951).
When we were publishing in the 1970's we were still calling it the
'Roothaan-Hall' LCAO-MO method.
and BTW for my younger American colleagues: it is not pronounced "Ruth-Ann".
Luke
-- 
Luke A. Burke           
Professor and Chair, Department of Chemistry
Rutgers University, Camden, NJ08102, USA
tel: 609-225-6158/6142;fax:-6506
---------------------
Subject: Re: CCL:The "birth-year" of computational chemistry?
Date: Wed, 01 Mar 2000 15:50:25 -0300
From: Roy Edward Bruns <[email-masked]>
To: Lingran Chen <[email-masked]>

Dear Dr. Chen,
     No, the authors of the paper I mentioned did not state specifically
what  computer they used but they do describe IBM computing equipment.
They also make a reference to a book by W. J. Eckert, Punched card methods
in Scientific computation 

(Thomas J. Watson
Astronomical Computing Bureau, Columbia University, New York, 1940).
I look forward to receiving your summary.
Best wishes,
Roy Bruns

Lingran Chen wrote:

> Dear Prof. Bruns:
> Thank you again for your message. That's very interesting.
>
> As you know, the first general-purpose computer -
> ENIAC (Electronic Numerical Integrator and Computer)
> was invented in 1946.
> Did that article mention which computer they were using?
> Kind regards,
> -Lingran
>
> Roy Edward Bruns wrote:
>>
>>Dear Dr. Chen,
>>    The article I referred to describes the calculation of line strengths and
>>positions in the rotational spectra of asymmetric rotors.  The authors are
>>well-respected spectroscopists.  You might be interested in reading the section of
>>the paper dealing with the calculations.  An interesting excerpt is:
>>
>>" In the International Business Machines all the quantities used in the calculations
>>are supplied on cards, their numbers or identification letters appearing as holes
>>punched in certain locations.  The machines read the information by brushes which
>>make electrical contacts through the holes as the cards run through the machine."
>>
>>The article goes on to describe the key punch, sorter, collator, reproducer,
>>multiplier and summary tabulator.
>>
>> Sincerely,
>> Roy Bruns
>>
>> Lingran Chen wrote:
>>
>>> Dear Prof. Bruns:
>>> Thank you very much for your message.
>>> What's the subject of the paper
>>> "J. Chem. Phys. 14 35 1946"?

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