X-ALPHA, DFT TODAY:SUMMARY



Thurs 2000 July 6
 Here is a summary of the answers to my X-alpha question. I thank all who
 responded (#1--#4).
 Question:
 > > Monday 2000 June 12
 > >
 > > Hello,
 > >
 > > the Xalpha method, developed by John slater (1951) mainly for solids
 and
 > > atoms, and used till at least the early 1970's , was perhaps the
 first
 > > really useful DFT method. For molecules it has now been replaced by
 > > Kohn-Sham-based approaches to DFT.
 > >
 > > (1) Is the Xalpha method still used for solids/crystals (e.g. by
 > > solid-state physicists?). If not, what replaced it?
 > > (2) In modern molecular DFT, probably the most popular method is
 > > B3LYP/6-31G*. What seems to be the second most widely-used?
 > >
 > > Thanks
 > > E. Lewars
 ====
 Answers
 #1
 Dr Robert J. Doerksen, rjd |-at-| bastille.cchem.berkely.edu
 > Dear Dr. Lewars,
 >
 >         I just have a small comment on (1):
 >         You may be amused by the article Dennis Salahub wrote giving a
 > retrospective on the X-Alpha method, in Theoretical Chemistry
 Accounts,
 > in their 20th century highlights issue:
 >
 > Dennis R. Salahub: From X<alpha>-scattered wave to end-of-the-century
 > applications of density functional theory in chemistry.  Perspective
 on
 > "Chemical bonding of a molecular transition-metal ion in a crystalline
 > environment" (Johnson KH, Smith FC Jr (1972) Phys Rev B 5: 831-843)
 >
 > That's in:       Theor Chem Acc 103 (2000) 3/4, 311-312
 >
 > Cheers,
 >
 >   Robert
 >
 > Dr. Robert J. Doerksen
 *************************************************
 > Head-Gordon Group
 *
 > Department of Chemistry                        work phone (510)
 642-9304
 > University of California                              fax (510)
 643-6232
 > Berkeley, CA, USA  94720         e-mail:
 rjd |-at-| bastille.cchem.berkeley.edu
 > **** webpage:
 http://www.cchem.berkeley.edu/~mhggrp/doerksen/rjdhome.htm
 ---
 #2
 Per-Ola Norrby, peo |-at-| dfh.dk
          Hi,
 >
 > >(2) In modern molecular DFT, probably the most popular method is
 > >B3LYP/6-31G*. What seems to be the second most widely-used?
 >
 >         I'd vote for BP86.  It's been around longer, is almost as
 > accurate, and substantially faster (at least in some codes...).
 >
 >         /Per-Ola
 > --
 >
 > ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^
 >   *  Per-Ola Norrby, Associate Professor
 >   *  The Royal Danish School of Pharmacy, Dept. of Med. Chem.
 >   *  Universitetsparken 2, DK 2100 Copenhagen, Denmark
 >   *  Tel.   +45-35306506, fax +45-35306040
 >   *  Email: peo |-at-| dfh.dk (preferred), peo |-at-| compchem.dfh.dk
 >   *  WWW:   http://compchem.dfh.dk/PeO/
 ------------
 #3
 Thomas Heine, Thomas.Heine |-at-| chiphy.unige.ch
 > (1) mainly LDA, later on GGA was used as well
 > (2) B3LYP is the mostly used by chemists, it is almost never used by
 > physicists, since (i) they don't like HF exchange since it makes the
 > programs very slow, (ii) it just works well for lighter elements.
 > Perdew-Wang 96, PW91 and the newer PBE is used quite often, I think in
 a
 > competitive amount with old-fashioned LDA (e.g. VWN).
 >
 > Thomas
 > University of Geneva
 >
 > PS: Let me know what others tell you
 ---------
 #4
 Thomas Bligaard Petersen, bligaard |-at-| fysik.dtu.dk
  Hello,
 >
 > I propose a response to question 1:
 >
 > The Xalpha was also replaced by the Kohn-Sham approch. In solid state
 physics the
 > LDA (of Kohn-Sham) was the most used exchange-correlation functional.
 The role was
 > taken over by the LSDA (Gunnarson and Lundquist) that describes
 magnetic systems
 > better. These are still used, and especially in more theoretical part
 of solid
 > state theory, as they are some of the only true ab-initio approches in
 DFT. For
 > applications the PW91 (Perdew-Wang) has become very important, as it
 corrects some
 > important deficiencies of the LDA. The PBE (Perdew-Burke-Ernzerhofer)
 removes
 > some problems of oscillating xc-potential in the PW91, whereby the
 numerical
 > behaviour of the calculations are somewhat improved. Other then that
 it yields
 > results very similar to PW91, and has more or less replaced the use of
 PW91 today.
 > The B3LYP yields quite bad results in solids, this is probably related
 to the
 > Hartree-Fock approch having some problems here. In the future orbital
 dependent
 > potentials are probably going to have growing importance in solid
 state physics,
 > but the selfconsistent implementation of these functionals are not yet
 in common
 > use, even if the functionals appear to give vastly improved results
 for some
 > systems. One such functional is the PKZB meta-GGA
 (Perdew-Kurth-Zupan-Blaha).
 >
 > In short the LSDA and the PBE are the most used today.
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