Summary: References on exact solutions to Schroedinger equations?



Dear CCLers:
 Some days ago I asked the following question:
 > Dear CCLers:
 >
 > I'm looking for the references about the mathematically *exact*
 > solutions to Schroedinger equations for any chemical systems.
 > Thanks in advance.
 >
 > -Lingran
 I have received many replies, which are summarized below.
 First, let me cite the answers of my question from Ira N. Levine's
 book "Quantum Chemistry" (5th edition, 2000) I just bought and
 received
 today:
 P.78: "We solved the Schroedinger equation exactly for the particle in a
 box and
 the harmonic oscillator."
 P.163: "The Schroedinger equation for the one-electron atom is exactly
 solvable.
 However, because of the interelectronic repulsion terms in the
 Hamiltonian, the
 Schroedinger equation for many-electron atoms and molecules is not
 separable in
 any coordinate system and cannot be solved exactly. "
 P.376: "The electronic Schroedinger equation for H2+ is separable, and
 we can get
 exact solutions for the eigenfunctions and eigenvalues."
 The answers I received are listed (in the order I received) below.
 Thanks a lot!
 -Lingran
 > ***********************************
 > Lingran Chen, Ph.D.
 > Senior Scientific Programmer
 > MDL Information Systems, Inc.
 > 14600 Catalina Street
 > San Leandro
 > CA 94577
 > U.S.A.
 >
 > Phone: (510) 895-1313
 > FAX:   (510) 614-3616
 >
 > Email: LCHEN;at;MDLI.COM
 > Web:   http://www.mdli.com
 > ***********************************
 -----------------------------------------------------------------------------------
 Subject:
             CCL:References on exact solutions to Schroedinger equations?
        Date:
             Wed, 02 Feb 2000 09:31:46 +0100 (CET)
       From:
             Jochen =?UNKNOWN?Q?K=FCpper?= <jochen;at;uni-duesseldorf.de>
         To:
             Lingran Chen <lchen;at;mdli.com>
         CC:
             "chemistry;at;ccl.net" <chemistry;at;ccl.net>
  References:
             1
 As far as I understand there are none :-( You could look at
 textbooks-solutions of H-atoms, though ).
 Jochen
 --
 Heinrich-Heine-Universität
 Institut für Physikalische Chemie I
 Jochen Küpper
 Universitätsstr. 1, Geb. 26.43.02.29
 40225 Düsseldorf, Germany
 phone ++49-211-8113681, fax ++49-211-8115195
 http://www.jochen-kuepper.de
 ----------
 Subject:
         Re: CCL:References on exact solutions to Schroedinger equations?
    Date:
         Wed, 02 Feb 2000 11:40:35 +0200 (EET)
    From:
         John Kerkines <jkerk;at;arnold.chem.uoa.gr>
      To:
         Lingran Chen <lchen;at;mdli.com>
 Dear Lingran,
 That's a very interesting question you sent to the list. Can you please
 forward to me (or to the list) any responses?
 With Regards,
 John Kerkines
 ----------
 Subject:
              CCL:References on exact solutions to Schroedinger
 equations?
         Date:
              Wed, 02 Feb 2000 15:50:19 +0100
        From:
              Thomas Bligaard Pedersen <bligaard;at;fysik.dtu.dk>
  Organization:
              Physics Department, Techn. Univ. of Denmark
          CC:
              Lingran Chen <lchen;at;mdli.com>,
 "chemistry;at;ccl.net"
 <chemistry;at;ccl.net>
   References:
              1 , 2
 The only molecules, for which there exists exact analytical solutions,
 are the
 molecular ions of homonuclear diatomics with only one electron: H2(+),
 He2(3+),
 >...
 "Where as the equation for the H atom is separable in sperical polar
 coordinates,
 the equation for the molecule-ion is separable in ellipsoidal
 coordinates in which
 the two nuclei are the foci of the ellipses."
 quote P.W.Atkins, Molecular Quantum Chemistry 2nd ed. p 250-251
 An actual derivation is not made in this book, but I have seen one in
 lecture
 notes by Jens Peder Dahl. These might be difficult to obtain, but he is
 very
 helpfull, and can probably direct you to the original references if you
 contact
 him on
 jpd;at;kemi.dtu.dk
 I hope this helps
 Thomas
 ----------
 Subject:
         mathematically exact
    Date:
         Wed, 02 Feb 2000 08:02:06 -0800
    From:
         vmohan;at;isisph.com
      To:
         LCHEN;at;MDLI.COM
 Hi,
 I would think that Quantum Monte Carlo method yields the
 mathematically exact solutions to Schrodinger equation.
 The advantage of this method is that the correlation term [exp(-rij)]
 can be directly used in the wavefunction.  Conventional variational
 methods include the electron correlation indirectly.
 The exactness of QMC on a number of chemical systems thas been
 published by Jim Anderson [Penn.State].
 Hope this helps,
 -mohan
 ----------
 Subject:
              Re: CCL:References on exact solutions to Schroedinger
 equations?
         Date:
              Wed, 02 Feb 2000 08:14:03 -0800
        From:
              wsteinmetz <wsteinmetz;at;POMONA.EDU>
  Organization:
              Pomona College
          To:
              Lingran Chen <lchen;at;mdli.com>
   References:
              1
 Mathematically exact solutions?
 The list of closed-form analytic solutions is VERY short.  The list of
 chemical
 problems includes the
 H atom, the harmonic oscillator, the rigid rotor, possibly the Morse
 potential, and
 the ESR/NMR problem.
 Consult Pauling and Wilson, Introduction to Quantum Mechanics.  Another
 good
 practical book with solutions
 is S. Flueege, Practical Quantum Mechanics, Springer-Verlag.  Any good
 book on NMR
 will outiline the application
 of angular momentum theory to the calculation of the spectrum of a
 system of
 coupled spins.  The classic was written
 by Pople, Schneider, and Bernstein.  The solution involves the
 diagonalization of N
 x N matrices.
 ----------
 Subject:
         Re: CCL: References on exact solutions to Schroedinger equation
    Date:
         Wed, 02 Feb 2000 11:54:39 -0500 (EST)
    From:
         Stefan Fau <fau;at;qtp.ufl.edu>
      To:
         lchen;at;mdli.com
 Hi,
 it may not be what you are looking for, but maybe two years ago some
 mathematician found an exact solution to the three body interaction
 problem, I think by developing it in an infinite series. I believe I
 read it as a short note in Scientific American.
 Stefan
 ______________________________________________________________________
 Dr. Stefan Fau                  fau;at;qtp.ufl.edu
 Quantum Theory Project
 University of Florida
 Gainesville FL 32611-8435
 ----------
 Subject:
             Re: CCL:References on exact solutions to Schroedinger
 equations?
        Date:
             Wed, 02 Feb 2000 09:41:55 -0800
       From:
             "Richard P. Muller" <rpm;at;wag.caltech.edu>
         To:
             Lingran Chen <lchen;at;mdli.com>,
 "chemistry;at;ccl.net"
 <chemistry;at;ccl.net>
  References:
             1 , 2 , 3
 Thomas Bligaard Pedersen wrote:
 >
 > The only molecules, for which there exists exact analytical solutions,
 are the
 > molecular ions of homonuclear diatomics with only one electron: H2(+),
 He2(3+),
 > >...
 >
 > "Where as the equation for the H atom is separable in sperical polar
 coordinates,
 > the equation for the molecule-ion is separable in ellipsoidal
 coordinates in which
 > the two nuclei are the foci of the ellipses."
 > quote P.W.Atkins, Molecular Quantum Chemistry 2nd ed. p 250-251
 > An actual derivation is not made in this book, but I have seen one in
 lecture
 > notes by Jens Peder Dahl. These might be difficult to obtain, but he
 is very
 > helpfull, and can probably direct you to the original references if
 you contact
 > him on
 >
 > jpd;at;kemi.dtu.dk
 >
 > I hope this helps
 If you're interested in close-to-exact solutions, I would suggest
 looking at the papers of Hylleraas or Pekeris for the He atom (I can
 send you software that reproduces Pekeris' work, if you'd like).
 I also highly recommend Flugge's _Practical_Quantum_Mechanics_, which
 has a wide variety of problems solved analytically. Bethe and Jackiw'w
 _Intermediate_Quantum_Mechanics_ is also quite good for this.
 --
 Richard P. Muller, Ph.D.
 rpm;at;wag.caltech.edu
 http://www.wag.caltech.edu/home/rpm
 ----------
 Subject:
             CCL:References on exact solutions to Schroedinger equations?
        Date:
             Wed, 02 Feb 2000 18:52:28 +0100
       From:
             Eberhard von Kitzing <vkitzing;at;MPImF-Heidelberg.mpg.de>
         To:
             Thomas Bligaard Pedersen <bligaard;at;fysik.dtu.dk>
         CC:
             Lingran Chen <lchen;at;mdli.com>,
 "chemistry;at;ccl.net"
 <chemistry;at;ccl.net>
  References:
             1 , 2
 At 15:50 Uhr +0100 02.02.2000, Thomas Bligaard Pedersen wrote:
 >The only molecules, for which there exists exact analytical solutions,
 are the
 >molecular ions of homonuclear diatomics with only one electron: H2(+),
 >He2(3+),
 >>...
 >
 >"Where as the equation for the H atom is separable in sperical polar
 >coordinates,
 >the equation for the molecule-ion is separable in ellipsoidal
 coordinates
 >in which
 >the two nuclei are the foci of the ellipses."
 You may find something in
 Hund Z Phys 36, 657 (1926)
 Mulliken J Chem Phys 3, 375 (1935)
 Coulson Trans Farad Soc 33, 1479 (1937)
 ==========================================================
 Eberhard von Kitzing
 Abteilung Zellphysiologie
 Max-Planck-Institut fuer Medizinische Forschung
 Jahnstr. 29
 D 69120 Heidelberg        Tel: +49 6221 486 467
 Germany                   FAX: +49 6221 486 459
 email: vkitzing;at;mpimf-heidelberg.mpg.de
 WWW: http://sunny.mpimf-heidelberg.mpg.de/people/vkitzing/
 ----------
 Subject:
             CCL:References on exact solutions to Schroedinger equations?
        Date:
             Wed, 02 Feb 2000 13:27:49 -0600
       From:
             "Robert E. Harris" <HarrisR;at;missouri.edu>
         To:
             Chemistry <chemistry;at;ccl.net>
  References:
             1 , 2
 The H2 molecule positive ion solution is discussed on pp. 201-203 of
 Eyring, Walter, and Kimball's book, "Quantum Chemistry".  They refer
 to
 work;  E. Teller, Z. Physik, 61, 458 (1930), O. Burrau, Kgl. Danske
 Videnskab. Selskab., 7, 1 (1927), E. Hylleras, Z. Physik, 71, 739
 (1931),
 and G. Jaffe, Z. Physik, 87, 535 (1934).  It is also discussed on pp.
 134-136 of Pitzer's "Quantum Chemistry".  See also pp. 1-40 of
 Slater's
 "Quantum Theory of Molecules and Solids, Volume 1, Electronic Structure
 of
 Molecules".  Slater says quite complete numerical information about the
 solution is given by D. R. Bates, K. Ledsham, and A. L. Stewart, Phil.
 Trans. Roy. Soc. London, 246, 215 (1953).
 One should note that the solution for the ground state is not closed
 form
 in terms of elementary transcendental functions.
 REH
 Robert E. Harris  Phone: 573-882-3274  Fax:  573-882-2754
 Department of Chemistry, University of Missouri-Columbia
 Columbia, Missouri, USA 65211
 ----------
 Subject:
             CCL:References on exact solutions to Schroedinger equations?
        Date:
             Wed, 02 Feb 2000 13:40:54 -0600
       From:
             "Robert E. Harris" <HarrisR;at;missouri.edu>
         To:
             chemistry;at;ccl.net
  References:
             1 , 2
 I neglected Pauling and Wilson's "Introduction to Quantum Mechanics",
 pp.
 327-340 in the Dover reprint.
 The exact solutions for H2+ ion are of course numerical solutions; these
 are exact in the sense that the exponential solution for the H atom is
 exact.  The exponential function is well-know and frequently tabulated,
 while the solutions to the H2 + ion are not familiar.  So, some would
 say
 the H atom is solved "exactly" while the H2 + ion isn't, but really,
 is
 a
 mutt more of a dog than an Afgan ound jsut because mutts are more
 familiar?
 REH
 Robert E. Harris  Phone: 573-882-3274  Fax:  573-882-2754
 Department of Chemistry, University of Missouri-Columbia
 Columbia, Missouri, USA 65211
 ----------
 Subject:
         Exact Solutions to "Chemical Systems"
    Date:
         Wed, 02 Feb 2000 15:44:11 -0500 (EST)
    From:
         Brian Williams <williams;at;bucknell.edu>
      To:
         lchen;at;mdli.com
 I don't know if this is exactly what you are after, but at the moment I
 think I have a way to define analytically solvable potentials resembling
 diatomic or Morse potential curves. I am at the moment attempting to see
 if
 these analytically exact solutions can be fit to experimental data for
 diatomics. I do not have this work written up, but would be happy to
 send
 you notes if you are interested.
 Brian Williams, Chemistry
 Bucknell University
 ----------
 Subject:
         Exact solutions.
    Date:
         Thu, 03 Feb 2000 01:35:43 +0100
    From:
         Thomas Bligaard Pedersen <bligaard;at;fysik.dtu.dk>
      To:
         lchen;at;mdli.com
 I was wrong in saying that only homonuclear diatomics
 are solved analytically. These were solved in
 G. Jaffé, Z. Phys. 87:535 (1934)
 Heteronuclear diatomic molecular ions with one electron
 are also solved:
 W.G.Barber and H.R.Hassé, Proc. Camb. Phil. Soc. 31:564
 (1935)
 Thomas
 ----------
 Subject:
         CCL:Nuclear Attraction Integrals
    Date:
         Thu, 03 Feb 2000 09:42:45 +0100 (MET)
    From:
         Christoph.van.Wuellen;at;ruhr-uni-bochum.de
      To:
         rpm;at;wag.caltech.edu (Richard P. Muller)
     CC:
         chemistry;at;ccl.net
 A nuclear attraction integral is just a special case of a two-electron
 integral:
 <i | 1/(r-c) | j> = (ij | kk)
 where k is a normalized s-Funktion centered at c with "infinitly high"
 exponent. Some simplifications arise naturally, so if you have a text
 on two-electron integrals, it also covers nuclear attr. integrals.
 ---------------------------+------------------------------------------------
 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:
 Christoph.van.Wuellen;at;Ruhr-Uni-Bochum.de
 ---------------------------+------------------------------------------------
 ----------
 Subject:
         CCL:Re, References on exact solutions ...
    Date:
         Thu, 03 Feb 2000 09:49:32 +0100 (MET)
    From:
         Christoph.van.Wuellen;at;ruhr-uni-bochum.de
      To:
         chemistry;at;ccl.net
 I wonder if during this discussion is has been pointed out that H2+ is
 a three-body system. The "exact" solution discussed so far is however
 the
 solution of a one-body Schroedinger equation with the clamped nuclei
 hamiltonian.
 ---------------------------+------------------------------------------------
 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:
 Christoph.van.Wuellen;at;Ruhr-Uni-Bochum.de
 ---------------------------+------------------------------------------------
 ----------
 Subject:
         CCL:Re, References on exact solutions ...
    Date:
         Thu, 03 Feb 2000 23:18:22 +0200 (EET)
    From:
         Tom Sundius <sundius;at;pcu.helsinki.fi>
      To:
         Christoph.van.Wuellen;at;ruhr-uni-bochum.de
     CC:
         chemistry;at;ccl.net
 On Thu, 3 Feb 100 Christoph.van.Wuellen;at;ruhr-uni-bochum.de wrote:
 > I wonder if during this discussion is has been pointed out that H2+ is
 > a three-body system. The "exact" solution discussed so far is
 however
 the
 > solution of a one-body Schroedinger equation with the clamped nuclei
 > hamiltonian.
 Of course there is no analytical solution to a three-body problem.
 But a complete numerical solution by separation of the variables was
 already given in 1927 by Oyvind Burrau in Denmark. His solution to the
 problem in the book by Pauling and Wilson (Introduction to Quantum
 Mechanics, sect. 42c). This solution was later improved by Hylleraas
 and Jaffe. The results were in very close agreement with experiment.
 Tom Sundius
 University of Helsinki, Department of Physics    phone +358-9-191 8339
 P.O.Box 9, FIN-00014 Helsinki, Finland           fax   +358-9-191 8680
 ----------
 Subject:
              CCL:Re, References on exact solutions ...
         Date:
              Fri, 04 Feb 2000 11:32:36 +0100
        From:
              Ramon Crehuet <rcsqtc;at;iiqab.csic.es>
  Organization:
              C.S.I.C.
          To:
              chemistry;at;ccl.net
   References:
              1
 There is system that can be considered somehow chemical: Hooke's atom.
 It consists
 of an atom with two Coulomb interacting electrons bounded to a nucleus
 by an
 harmonic potential.
 This is very briefly described by Burke, Perdew and Ernzerhof in J.
 Chem. Phys,
 Vol. 109, No. 10, p. 3760 and the mathematical solution can be found in
 references
 therein.
 SORRY!!!
 Vol. 109, No. 10, p. 3760, 1998
 Ramon
 ----------
 Subject:
         CCL:Re, References on exact solutions ...
    Date:
         Fri, 04 Feb 2000 12:15:46 +0100
    From:
         assfeld;at;host23.lctn.u-nancy.fr
      To:
         chemistry;at;ccl.net, rcsqtc;at;iiqab.csic.es
 Any FULL CI calculations are *exact* solutions, at least for the basis
 set considered. And there is a lot of litterature about it.
 Just my 2 cents...
                         ...Xav
 http://www.lctn.u-nancy.fr/Chercheurs/Xavier.Assfeld