***************************************************************
**** ****
**** ESF Programme ****
**** ****
**** RELATIVISTIC EFFECTS IN HEAVY ELEMENT CHEMISTRY ****
**** AND PHYSICS ****
**** ****
***************************************************************
Newsletter No. 23 (February 18, 1997)
______________________________________________________________
Editor: Bernd Hess, hess@uni-bonn.de
Tel. 49-228-732920
FAX 49-228-732551
______________________________________________________________
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)
J. Karwowski (Torun)
P. Pyykko (Helsinki, Chairman)
K. Schwarz (Vienna)
A. Sgamellotti (Perugia)
C. Werner (ESF).
================================================================================
--- 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 (#24) is scheduled for April 1997.
Please send material >by e/mail< that enables us to fill the
following topics in forthcoming newsletters
All REHE newsletters are available on www under URL
http://pcgate.thch.uni-bonn.de/tc/hess/esf/nl.html
see also the URL of the European Science Foundation
http://www.esf.c-strasbourg.fr
================================================================================
--- 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 #16
for details.
Please indicate >who wants to go >when >where, >what shall be done and
>how much money (in FRF) is required.
As a rule, the steering committee members will decide on the applications
on occation of ther meetings.
Applications for visits that require decision in the interim time between
steering committee meetings may still be handled by means of consultation
within the steering group.
After the journey, a short report about the scientific accomplishments
is required. Please send a version by e-mail in a form suitable for
publication in a REHE newsletter to hess@uni-bonn.de
Should the planned dates of your stay change for any reason, you are
requested to notify the Chairman and the Vice-Chairman (preferrably by
e-mail) 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 Alexander A. Bagatur'yants]
Report on a scientific visit of Alexander A. Bagatur'yants (Institute of
Chemical Physics, Russian Academy of Sciences, Moscow, Russia) to Professor
Evert Jan Baerends (Scheikundig Laboratorium der Vrije Universiteit,
Amsterdam, The Netherland)
from September 15 to December 14, 1995.
The project was devoted to relativistic density functional study of the
electronic and geometrical structure of small silver and gold sulfide
clusters (M2S)n, n = 1 and 2 and 18-crown-6 complexes with Ag+, Hg++, Ag0,
Hg+, Hg0, AgNO3, and HgX2 (X= Cl, Br, and I).
Previously, detailed ab initio pseudopotential calculations on the
geometrical and electronic structure of monomers and dimers of silver and
gold sulfides Ag2S, Au2S, (Ag2S)2, and (Au2S)2 have been performed at
Stuttgart University in collaboration with Prof. H. Stoll and Prof. H.-J.
Werner (see Newsletter No. 18 (April 18, 1996) for more details).
Within the present project, the electronic and geometrical structure of
small silver and gold sulfide clusters Ag2S, Au2S, Ag4S2, and Au4S2 has been
calculated using density functional theory (DFT). The calculations are
performed with the Amsterdam density functional (ADF) program package. The
DFT Hamiltonian contains the Vosko-Wilk-Nusair parametrization for the local
density part (LDA), and the Becke and the Perdew-Wang nonlocal gradient
corrections for the exchange part (Becke88) and for the correlation part
(PW91) of the exchange-correlation potential. The core shells comprise up to
and including the 2p shell for S, the 4p shell for Ag, and the 5p shell for
Au, and the core electrons are taken to be frozen in the calculations. Two
Slater-type basis sets, one of the double-zeta quality (ADF, basis set II)
and the other one of the triple-zeta quality with polarization functions
(ADF, basis set IV) are used in the calculations. The relativistic effects
are taken into account with the use of the quasi-relativistic Pauli
Hamiltonian. The results obtained are compared with the results of
previously performed calculations on the same clusters with the use of ab
initio LCAO method in the Gaussian basis set at the correlated level with
the use of relativistic pseudopotentials. A great difference is found in the
calculated dipole moments of the Ag2S and Au2S monomers. The LCAO method
predicts 5=7.4 D for Ag2S and 5=5.1 D for Au2S, whereas DFT gives 5=4.9 D
for Ag2S and 5=3.2 D for Au2S with basis set II and 5=4.3 D for Ag2S and
5=2.6 D for Au2S with basis set IV. The relative stability of dimeric
structures obtained within the two approaches rather correlates rather well
in the case of Ag4S2, but the results are different for Au4S2. The nature of
these discrepancies is discussed and partly related to the basis set
effects.
In addition, preliminary comparative band structure calculations have been
performed for Li2S and Au2S in order to estimate the reliability of
relativistic DFT approach for sulfide structures. The results gives a
satisfactory agreement for the lattice constant of Li2S but the lattice
constant of Au2S is somewhat overestimated.
Density functional theory (DFT) have also been used for molecular simulation
of the electronic and geometrical structure of 18-crown-6 and its complexes
with Ag+, Hg++, Ag0, Hg+, Hg0, AgNO3, and HgX2 (X= Cl, Br, and I). The
calculations are performed with the Amsterdam density functional (ADF)
program package. The density functional Hamiltonian contains the Vosko-Wilk-
Nusair parametrization for the local density part (LDA), and the Becke and
the Perdew-Wang nonlocal gradient corrections for the exchange part
(Becke88) and for the correlation part (PW91) of the exchange-correlation
potential. The relativistic effects are taken into account with the use of
the quasi-relativistic Pauli Hamiltonian. The core shells comprise up to and
including the 1s shell for C, O, and N, the 2p shell for Cl, the 3p shell
for Br, the 4p shell for I and Ag, and the 5p shell for Hg, and the core
electrons are taken to be frozen in the calculations. The Slater-type basis
set of the triple-zeta quality with polarization functions (ADF, basis set
IV) is used in the calculations and full geometry optimization is performed
for all the structures under consideration. The resulting structure of
complexes is analyzed and compared with the experimental crystal structure
data. The complexation energies are analyzed in terms of various
contributions including Pauli and electrostatic repulsion and orbital
interactions. Both vertical and adiabatic electron affinities are calculated
for 18-crown-6 complexes with the metal ions. It is found that complexes
with neutral Ag and Hg atoms are unstable with respect to dissociation into
the free metal atom and the crown ether molecule. The complexation energy
decreases in the sequence AgNO3 > HgCl2 > HgI2 > HgBr2.
All the results were presented at the international symposium "Computer
Assistance to Chemical Researches" held on December 17-18 in Moscow, Russia.
I am very grateful to Prof. E.J. Baerends and other members of the
theoretical group for help, fruitful discussions and very kind hospitality.
I would like to thank the European Science Foundation and the REHE Steering
Committee for the financial support that made this visit possible.
Alexander Bagatur'yants
++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++
================================================================================
--- 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.
++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++
[communicated by Pekka Pyykko]
REPORT ON THE REHE WORKSHOP W4-96,
"Determination of Nuclear Quadrupole Moments"
The workshop took place at the Department of Chemistry,
University of Helsinki, Finland, on 9-11 December, 1996.
There were nine lecturers and thirty other participants
(distributed as: Austria 2, Chile 1, Denmark 2, Estonia 1,
Finland 19, France 1, Germany 2, Israel 1, Italy 1, Nether-
lands 1, Poland 2, Slovakia 1, Spain 1, Sweden 2 and Russia 2).
Six poster contributions were also shown.
The central point is that a combination of spectroscopic
nuclear quadrupole coupling constants, eqQ/h, in atoms, molecules
or solids with careful calculations of the electric-field
gradient (EFG), q, is now one of the best ways to determine
nuclear quadrupole moments, Q.
The event was started by 'Introduction to quadrupole effects'
by P. PYYKKO" (Helsinki). The appropriate relativistic
corrections were emphasized. L. LABZOWSKY (St. Petersburg)
covered the QED background and described the "dynamical" model
of (M1, E2 or M3) hyperfine interactions for highly ionized
atoms. In this model, both the electrons and the 'valence protons'
of the nucleus are described by their respective Dirac
equations.
U. KALDOR (Tel Aviv) presented the relativistic coupled-cluster
approach. The present problem will require either a finite-
field treatment or a Lambda-operator (Z-vector) approach.
J. BIERON (Cracow) covered the MCDF approaches. Among others,
a new Q(Sc) was reported. J. OLSEN (Lund) lectured on the
large MCHF calculations using the LUCAS and LUCIA codes;
'large' meaning in this case up to 4*10**9 Slater determinants.
It should be emphasized that most of the current Q-values in
the range Be -- Ca come from this finite-element source.
He also pointed out the lack of convergence of the MPn series
for very high 'n', for several highly stable systems.
L. VISSCHER (Odense) described his four-component Coupled-
Cluster code for molecules. Particularly interesting were the
preliminary estimates for spin-orbit effects on the halogen
q in hydrogen halides. These would change the quasirelativistic
Q(Br) and Q(I) of Kello" and Sadlej; the same 'spin-orbit tilting'
effect was treated semiempirically by Seth and Pyykko".
K. SCHWARZ (Vienna) gave a thorough introduction to their
solid-state DFT LAPW calculations in solids, including both
simple systems such as certain elements, and complicated ones,
like the YBCO superconductor. A new Q(Fe) for the iron
Moessbauer state was presented.
V. KELLO" (Bratislava) gave a comprehensive review on the Q-
values currently obtained from molecules (apart from H-2 or F-19m,
Li, (N), Na, (Cl), Br, I.
L. HEMMINGSEN (Danish Agricultural University) discussed the
nuclear quadrupole interactions (NQIs) of Cd-111m-labelled
metalloproteins and model complexes.
It turned out that all lecturers emphasized their method of
calculation, in addition to the specific problem at hand.
Special thanks are due to Dr. Dage Sundholm and Mrs. Susanne
Lundberg for performing most of the administrative work.
Pekka Pyykko"
++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++
[communicated by Bernd Hess]
EUROPEAN RESEARCH CONFERENCES
RESEARCH CONFERENCE ON
RELATIVISTIC EFFECTS ON STRUCTURE, DYNAMICS AND SPECTROSCOPY
>>> March 8, 1997 - March 13, 1997 in the <<<
>>> Hotel Alixares del Generalife in Granada (Spain) <<<
Chairman: Bernd Artur Hess (Bonn, Germany)
Vice-chairman: Jens Oddershede (Odense, Denmark)
---
--- Close to 100 participants have registered
--- The list of speakers and the titles of the lectures is given below
---
Jacek Karwowski (Torun, Poland) :
Relativistic Calculations with Explicitly Correlated Wavefunctions
Werner Kutzelnigg (Bochum, Germany) :
Relativistic Many-Electron Hamiltonians and Unexpected Singularities
Andrzej Sadlej (Lund, Sweden) :
Regular Two/One-Component Methods of Arbitrary High Accuracy in
$\alpha^2$
Jens Peder Dahl (Lyngby, Denmark) :
On the Dirac-Kepler Problem: The Johnson-Lippmann Operator,
Supersymmetry and Normal-Mode Representations
Hiroshi Nakatsuji (Kyoto, Japan) :
Relativistic Effects on NMR Shielding Constants
of Molecules Including Heavy Elements
Jens Oddershede (Odense, Denmark) :
Relativistic Calculations of Electric and Magnetic Properties of
Molecules
Vladimir Malkin (Bratislava, Slovakia) :
Spin-Orbit Correction to NMR Shielding Constants
From Density Functional Theory
Christian Teichteil (Toulouse, France) :
Spin-Orbit Pseudopotential Treatments
Paolo Palmieri (Bologna, Italy) :
Configuration Interaction Techniques
for Electron-Spin-Dependent Properties
Christel Marian (Bonn, Germany) :
Spin--Orbit Coupling in Unsaturated Transition Metal Compounds
Boris Minaev (Cherkassy, Ukraine) :
Spin-Orbit Coupling Effects in Organic Chemistry
and Spin Catalysis Phenomena
David Yarkony (Baltimore, Maryland, USA) :
The Effect Heavy Atom Spin-orbit Interactions on Predissociation
Hans Joachim Werner (Stuttgart, Germany) :
Spin-orbit Coupling Effects in Inelastic Collisions
and Elementary Reactions
Stanislav Biskupi\u c (Bratislava, Slovakia) :
Systematic Generation of Generally Contracted
Relativistic Gaussian Basis Sets
Arne Haaland (Oslo, Norway) :
The Gas-phase Structures of Simple Compounds
of Sixth Period Elements
Pekka Pyykk\"o (Helsinki, Finland) :
Relativistic Contributions to Hyperfine Effects
and Intermolecular Interactions
Lester Andrews (Charlottesville, Virginia, USA) :
Matrix Infrared Spectra of Heavy Metal Hydrides
as a Probe of Relativistic Effects
Svetlana Malinovskaya (Odessa, Ukraine) :
Relativistic Calculation of the Quasimolecular Terms of the Na--Ne
System as an Active Medium for X-Ray Lasing
Peter Schwerdtfeger (Auckland, New Zealand) :
Large Relativistic Effects in Properties of Superheavy Elements
and Their Compounds
Evert Jan Baerends (Amsterdam, Netherlands) :
A Regular Two-Component Relativistic Hamiltonian for Coulomb
potentials. Relativistic DFT results for heavy element compounds
Ken Dyall (Moffett Field, California, USA) :
Interfacing Relativistic and Nonrelativistic Methods:
A Systematic Sequence of Approximations
Hubert Ebert (Munich, Germany) :
Magneto-Optical Phenomena in Transition Metal Systems
Balasz Gyorffy (Bristol, United Kingdom) :
Relativistic Effects in the Superconducting State
Zoila Barandiaran (Madrid, Spain) :
Relativistic Effects on the Structure and Spectroscopy of
Local Defects in Ionic Crystals
++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++
================================================================================
--- 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
++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++
[communicated by Martin Kaupp]
Interpretation of 13C NMR chemical shifts in halomethyl cations.
On the importance of spin-orbit coupling and electron correlation"
M. Kaupp, O. L. Malkina, V. G. Malkin Chem. Phys. Lett. 1996, 265, 55-59
++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++
[communicated by Jacek Karwowski]
N. Flocke, M. Barysz, J. Karwowski and G.H.F. Diercksen,
"Symmetric Group Approach to Relativistic CI":
I. "General Formalism", Int. J. Quantum Chem. 61 (1997) 1-10
II. "Reduction of Matrices in the Spin Space", ibid., 11-20
III. "Matrix Elements for Spin-Dependent Operators", ibid., 21-34
++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++
[communicated by Boris Minaev]
Dear Bernd,
I am sending some references to my papers. Though they are not funded by REHE,
they should be of interest for the REHE community.
1. B. F. Minaev, S. Knuts, H. Agren. On the interpretation of the exernal
heavy atom effect on singlet-triplet transitions. Chem. Phys. 181: 15-28, 1994.
2. B. F. Minaev, D. Jonsson, P. Norman, H. Agren. Character and spectra of triplet states in short polyenes. Chem. Phys. 194:19-31, 1995.
3. B. F. Minaev, S. Knuts, H. Agren. Response Theory Studies of triplet-singlet spectra and radiative lifetimes of naphthalene, quinoxaline and phthalazine. J. Phys. Chem. 98: 3943-3949, 1994.
4. B. F. Minaev, D. Jonsson, P. Norman, H. Agren. Response theory calculations of singlet-triplet trabsitions in molecular nitrogen.
Chem. Phys. 190:11-29, 1995.
5. B. F. Minaev, O. Vahtras, H. Agren. Magnetic phosphorescence of molecular
oxygen. Chem. Phys. 208:299-311, 1996.
6. H. Agren, O. Vahtras, B. Minaev. Response theory calculations of spin-orbit
coupling phenomena in molecules. Adv. Quant. Chem. 27:71-162, 1996
7. B. F. Minaev, H. Agren. Spin-orbit coupling induced chemical reactivity
and spin-catalysis phenomena. Collect. Czech. Chem. Commun. 60:340-371, 1995.
8. B. F. Minaev, H. Agren Spin catalysis of ortho-para hydrogen conversion.
J. Phys. Chem. 99: 8936, 1995.
9. B. F. Minaev, H. Agren. Spin-catalysis phenomena. IJQC, 57:519-532, 1996.
10. B. F. Minaev. Paramagnetic spin catalysis of a radical recombination
reaction. Mol. Engineering 6: 261-279, 1996.
++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++
--- P O S I T I O N S available
++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++
[no material for this section in the current newsletter]
++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++
================================================================================
--- P O S I T I O N S sought
++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++
[no material for this section in the current newsletter]
++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++
================================================================================
--- ADDRESS LIST
The REHE address list comprises 191 scientists as of February 18, 1997; the
next address list will be provided with newsletter no. 25
This newsletter is mailed to all collegues presently in the REHE mailing
list.
In order to join the REHE mailing list, please complete the form below
and send it back per e-mail to hess@uni-bonn.de
>>> 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. 23