*************************************************************** **** **** **** ESF Programme **** **** **** **** RELATIVISTIC EFFECTS IN HEAVY ELEMENT CHEMISTRY **** **** AND PHYSICS **** **** **** *************************************************************** Newsletter No. 14 (23. August 1995) ______________________________________________________________ Editor: Bernd Hess, hess@uni-bonn.de Tel. 49-228-732920 FAX 49-228-732251 ______________________________________________________________ The programme 'Relativistic Effects in Heavy-Element Chemistry and Physics' ('REHE') has been initiated by the European Science Foundation in November 1992 and it is expected to run for 5 years, i.e. from 1993 through 1997. The programme is intended to strengthen the in- dicated "field" and to facilitate interactions between European scientists concerned with related topics. The 'Steering Committee' of the programme has at present the following members: E. J. Baerends (Amsterdam) J.P. Daudey (Toulouse) K. Faegri (Oslo) I.P. Grant (Oxford) B. Hess (Bonn, Vice-Chairman) H. U. Karow (ESF) J. Karwowski (Torun) P. Pyykko (Helsinki, Chairman) K. Schwarz (Vienna) A. Sgamellotti (Perugia). ================================================================================ --- E D I T O R I A L Please send material for the forthcoming newsletter to my attention, hess@uni-bonn.de The newsletter will be sent out every second month around the 10th day of the month. Contributions should arrive in Bonn until the end of the preceding month. | The next newsletter (#15) is scheduled for Beginning of October 1995. | Please send your contributions until end of September 1995. Please send material >by e/mail< that enables us to fill the following topics in forthcoming newsletters All REHE newsletters are now available on www under URL http://pcgate.thch.uni-bonn.de/tc/hess/esf/nl.html ================================================================================ --- F E L L O W S H I P S In the framework of the REHE programme, there is support available for visits of doctoral students and also for senior scientists at institutions in a foreign partner country. This support covers visits lasting 2-4 months ("long-term visits") which will give the holders time to acclimatize to the methods used in the host laboratory as well as short visits ("short-term visits") of only a few days. Please send a short application detailing the project, the names of the scientists involved and the aproximate date and duration of the visit to either Pekka Pyykko or Bernd Hess. Please refer to REHE newsletter #7 for details. Should the planned dates of your stay change for any reason, you are requested to notify the Chairman as soon as possible with a copy to the ESF. ================================================================================ --- R E S E A R C H N E W S AND R E L A T E D I N F O R M A T I O N Summaries of recent research or comments to it (up to 1 page), which are of general interest to the 'REHE' community, may be submitted by any colleague preferrably by E-mail to my attention. ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ [communicated by Pekka Pyykko} RELATIVISTIC BIBLIOGRAPHY IN WWW The reference files of the two books: P. Pyykko", Relativistic Theory of Atoms and Molecules. A Bibliography 1916-1985, Lecture Notes in Chemistry 41, Springer-Verlag, Berlin, 1986, and P. Pyykko", Relativistic Theory of Atoms and Molecules. II. A Bibliography 1986-1992, Lecture Notes in Chemistry 60, Springer-Verlag, Berlin, 1993, as well as further references from 1993-94, altogether about 7600 items, can be freely consulted at the WWW address: www.csc.fi/lul/rtam/rtamquery.html. The literature analysis in the text part is only available in the books. ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ [communicated by Simon Faas] We would like to report on a paper titled "The ZORA formalisme applied to the Dirac-Fock equation" which is the result of a cooperation between the Universiteit Utrecht and the Vrije Universiteit (Amsterdam). It is written by S. Faas, J.G. Snijders J.H. van Lenthe, E. van Lenthe and E.J. Baerends and has recently been submitted to Chemical Physics Letters. In this paper the Zeroth Order Regular Approximation (ZORA), a two component approximation to the Dirac equation that was earlier formulated and tested within the framework of density functional theory (see van Lenthe et al. J. Chem. Phys. 99 (1993) 4597 and 101 (1994) 1272), is generalized to a treatment based on the Dirac-Fock equation. The performance of the ZORA equation and an improvement known as scaled ZORA is investigated, in particular with respect to orbital energies and various radial expectation values in the case of the Xenon and Radon atoms. The results of the simple ZORA approximation are shown to be quite close to the full Dirac-Fock method, except in the deep core region where the scaled version of the method is needed. It is found that a further approximation in which the density is calculated from the two-component ZORA orbitals alone gives very satisfactory results, which is an important result from a practical point of view since in this way one can avoid calculating any two-electron integrals involving small component basis functions. ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ [communicated by L. Pisani] Dear Prof. Hess, As requested, I summarize the results of the Cagliari-Groningen collaboration with Prof. W. C. Nieuwpoort, Dr. L. Visscher and Dr. B. de Jong of the University of Groningen in the week of 22-27 May 1995. The application No.11-95 in the REHE accounts was accepted on 28 April, 1995. The Dirac-Fock code MOLFDIR (developed in Groningen) has been installed in Cagliari and compared with the code MOREL (developed in Cagliari). Comparison of performances has been done at the SCF level. For high symmetry molecules, MOLFDIR performs much better because the MOREL code does not use symmetry to reduce the computational task. For non symmetric molecules, MOREL performs better because the separation between spin diagonal and non-diagonal two-electron integrals allows to discard a half of the integrals with a very small lost of accuracy and therefore to reduce by a factor of two the disk space and the SCF time. The possibility of reducing further the computational task for Dirac-Fock calculations has been discussed. While consideration on the small size of the positronic component has been proven very useful in neglecting two-electron integrals, still not much has been done to use the fact that the positronic component is very much concentrated around the nuclei. Very preliminary calculations seems to show that two-electron integrals LLSS with the two S orbitals on different centers may be neglected without affecting very much the molecular properties. I plan to use the MOLFDIR code to do more accurate tests. If the preliminary results will be confirmed, we can conclude that Dirac-Fock calculations on large molecules do not require a computational effort much larger than Hartree-Fock calculations. Yours sincerely Lorenzo Pisani ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ [communicated by Anatoli V. Titov] ***************************** Relativistic ECP calculations ***************************** Report on a scientific visit of Dr. Anatoli Titov (St.Petersburg Nuclear Physics Institute, Gatchina, St.Petersburg district, Russia) a group of Prof. Robert J. Buenker (Theoretische Chemie, Bergische Universitaet, Wuppertal, Germany) May 29 - June 02, 1995. During first two days of my visit I participated in the Colloquium of the German Science Foundation Schwerpunkt in Relativistic Effects in Heavy-Element Chemistry and Physics organised by Bernd Hess (May 29-30, Bonn) where I had fruitful discussions on the related topics. The second part of the visit I spent in Wuppertal working with the group of Prof. R.J.Buenker. We had extensive discussions with Prof. Buenker and Dr. A.B.Alekseyev on various aspects of the molecular calculations emloying relativistic effective core potentials (RECP): generation and gaussian approximation of RECPs, generation of gaussian basis sets for the corresponding pseudo-atoms, calculation of matrix elements with RECPs in molecular gaussian basis sets. I have presented our latest results on generation of the RECPs for precise molecular calculations and in turn was acquainted with the details of the relativistic CI method developed and used by Wuppertal's group. The main goal of this visit was to discuss joint work on molecular RECP calculations which we plan to do in September-October 1995 with the RECP versions developed in St.Petersburg (see, e.g., Phys.Rev.A, 50 (1994) 2239; I.I.Tupitsyn et al. "Generalized RECP in comparison with the conventional RECP method. Calculations for atoms Hg through Bi." - Preprint PNPI No.1954 (St.-Petersburg, 1994), 28 p.; J.Chem.Phys., express service; A.V.Titov et al.,"Self-Consistent RECP for Transition Metal Atoms: Cu, Ag and Au."-Structural Chemistry, Special issue: Current Trends in Computational Chemistry). Finally, I would like to thank Prof. R.J.Buenker and members of his group for useful discussions and hospitality which I met in Wuppertal. I would like to thank ESF and organizers of the REHE-network for the financial support making this visit possible. Anatoli Titov ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ [communicated by A. Rutkowski] Andrzej Rutkowski has been working with Prof. W.H.E. Schwarz at Siegen University from 23.05.95 till 30.06.95. We have been continuing the project "Effective Hamiltonian for Near-Degenerate States in Direct Relativistic Perturbation Theory". At first we finished for publication and submitted a corresponding theoretical paper to J. Chem. Phys. This manuscript presents the formalism (abstract available, and MS available as TEX files). The main task during my six weeks stay in Siegen was to apply the method to two-center one-electron model systems which have a large effective nuclear charge at small distances from the nucleus, with effective potential V = - [1 + A exp(-a*r**2) + B exp(-b*r**2) + ...]/r and which model the behaviour of MO-valence states of heavy molecules. I have also worked on the final version of the MS: "Regular Peturbation Theory of Relativistic Corrections. I. Basic Aspects" and submitted it to Phys. Rev. A (abstract available, and MS available as TEX files). ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ ================================================================================ --- P A P E R S F U N D E D B Y R E H E >>> please send a preprint of papers funded by REHE to Bernd A. He\ss, >>> Institut f\"ur Physikalische und Theoretische Chemie, Universit\"at Bonn, >>> 53115 Bonn, Germany Christian R. Hofmann and Gerhard Soff: Total and Differential Conversion Coefficients for Internal Pair Creation of Extended Nuclei (preprint) C. R. Hofmann, G. Soff, J. Reinhardt and W. Greiner: Angular correlations in internal pair conversion of aligned nuclei (preprint) for more information, contact hofmann@ptprs8.phy.tu-dresden.de P. Pyykko (J. Am. Chem. Soc. 117 (1995) 2067) : Predicted Chemical Bonds between Rare Gases and Au+ T.M. Greene, W. Brown, L. Andrews, A. Downs, G. Chertihin, N. Runeberg, P.Pyykko (J. Phys. Chem (1995) 7925) : Matrix Infrared Spectroscopic and ab Initio Studies of ZnH_2, CdH_2 and Related Metal Hydride Species ================================================================================ --- C O N F E R E N C E N E W S 'Conference News' (in general they should NOT overrun about 1 page) may be provided by organizers or their scientific secretaries. -- For meetings and workshops supported by ESF the submission of such a report is a m u s t . To facilitate my job the reports should be forwarded to my attention via E-mail. Also please send information about conferences that might be of interest for the members of the REHE community. ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ The REHE-workshop ****** Towards density functional theory of relativistic systems *** was organized by Professor R. Dreizler on May 27 and 28, 1995 in the Internationales Jugendforum, Bonn The workshop was structured by keynote lectures delivered by invited speakers, and short contributions by the participants of the workshop. The ample discussion time and the workshop atmosphere contributed to a marvellous exposition of anything you ever wanted to know about density functional theory, but were afraid to ask. 42 scientists from 9 countries attended. The conference started with an introduction by E. K. U. Gross (University of Wuerzburg) to the intricacies of non-relativistic DFT. R.O. Jones (Forschungszentrum Juelich) and W. H. E. Schwarz (University of Siegen) then focused on applications of NRDFT, discussing the question of which calculations can be made with DFT on which systems. J. Alonso (University of Valladolid) summarized the extensions of LDA by means of generalized gradient approximations. He reported on applications of the jellium model to alkali metal clusters, which prompted particularly lively discussions. R. Dreizler then gave an introduction to the state of the art in Relativistic Density Functional Theory, focusing on the fundamental aspects. E. Engel (University of Frankfurt) continued, reporting applications and details on the relativistic version of the Optimized Potential Method (OPM). Finally, X. Vinas (University of Barcelona) lectured about applications of DFT in Quantum Hadron Dynamics. The following short communications were presented and/or delivered as abstracts: M. Kaupp (Max-Planck-Institut fuer Festkoerperforschung): Ligand NMR chemical shifts in heavy-metal complexes via a combination of quasirelativistic pseudopotentials and DFT R. van Leeuwen, O.V. Gritsenko and E.J. Baerends (Vrije Universiteit Amsterdam) Analysis and modelling of Kohn-Sham potentials for atoms and molecules A. v. Kopylov, D. Heinemann, C. Duesterhoft, D. Kolb, N.A. Cordero (University of Kassel and Universidad de Valladolid): Density functionals under symmetry breaking density variations A.J. Sadlej (University of Lund) : Building the external perturbation dependence into density functionals A. Rutkowsky (Pedagogical University of Olsztyn) : Regular perturbation theory of relativistic corrections C. Capelle (University of Wuerzburg) : Spin-orbit effects in superconductors with heavy elements F. Calvayrac and E. Suraud (University of Toulouse) : Non-linear plasmon response in highly excited metallic clusters C.A. Ullrich and E.K.U. Gross (University of Wuerzburg) : Time-dependent density-functional approach to atoms in strong laser pulses C. van Wuellen (University of Bochum) : A relativistic density functional procedure by means of direct perturbation theory A.V. Titov (Petersburg Nuclear Physics Insitute) : Generalized relativistic effective core potentials Bernd Hess ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ ================================================================================ --- P O S I T I O N S available ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ [communicated by Ann-Marie Pendrill] PROFESSORSHIP ATOMIC AND MOLECULAR PHYSICS Applications are invited for the Chair of Atomic and Molecular Physics, with an emphasis on Atomic Physics at the School of Physics and Engineering Physics at Goteborg University and Chalmers University of Technology, Goteborg, Sweden The department has strong research activities both in experimental and theoretical atomic physics and the professor is expected to oversee and participate in both. The successful candidate should show a commitment to excellence in research as well as teaching and graduate student supervision. Previous knowledge of Swedish is not required. Closing time for the application will be September 25 1995. Persons interested in applying should contact Dr. Goran Niklasson, Dean of the School of Physics and Engineering Physics, S-412 96 Goteborg, Sweden (e-mail: tfsgn@fy.chalmers.se, phone +46 31 772 3194, fax +46 31 772 3202). Then you will obtain written particulars about the application. Information about the department can be found at the www-server http://www.fy.chalmers.se ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ ================================================================================ --- P O S I T I O N S sought ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ [no material for this section in the current newsletter] ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ ================================================================================ --- G O S S I P News about people visiting foreign laboratories, which could eventually faciliate invitations by a nearby lab. ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ [no material for this section in the current newsletter] ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ ================================================================================ --- ADDRESS LIST The REHE address list comprises 166 scientists as of Aug 23, 1995; the next address list will be provided with newsletter no. 16 In order to join the REHE mailing list, please complete the form below >>> PLEASE include TEL, FAX, E-MAIL <<< ================================================================= I am interested in receiving the REHE newsletter NAME ----------------------------------------------------------------- ADDRESS ----------------------------------------------------------------- ----------------------------------------------------------------- TEL ----------------------------------------------------------------- FAX ----------------------------------------------------------------- E-MAIL ----------------------------------------------------------------- MAIN RESEARCH INTERESTS ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ End of REHE Newsletter No. 14