Because of problems with my e-mail, I had to send this letter once more in order
to reach all recipients of the mailing list; sorry.
Bernd Hess
***************************************************************
**** ****
**** ESF Programme ****
**** ****
**** RELATIVISTIC EFFECTS IN HEAVY ELEMENT CHEMISTRY ****
**** AND PHYSICS ****
**** ****
***************************************************************
Newsletter No. 29 (March 24, 1998)
______________________________________________________________
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 ran for 5 years, i.e. from 1993 through 1997. The programme was intended
to strengthen the indicated "field" and to facilitate interactions between
European scientists concerned with related topics.
Apart from a few activities approved in 1997 and deferred to 1998, the programme
expired end of 1997. The 'steering committee' is now preparing the final report
for the European Science Foundation. 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
Dear collegues,
for the final report to the European Science Foundation, we have prepared
a list of 'papers funded by REHE'. We should like to include in this list
all those papers with REHE mentioned in the acknowledgement. This list
is now in the www, linked to the REHE newsletter pages at
http://pcgate.thch.uni-bonn.de/tc/hess/esf/nl.html
I should appreciate very much if you could visit this list and notify
me about any papers that should be included. Please, include the number
of the corresponding REHE project. Please send this information at
your earliest convenience (by email) to
hess@uni-bonn.de
and send me a reprint for those papers which are not mentioned.
-------------------------------------------------------------------------
The next newsletter (#30) is scheduled for June 1998.
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
================================================================================
--- 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 Andreas Savin]
Report on WENJIAN LIU's stay at the
Laboratoire de Chimie Theorique (CNRS)
Universite Pierre et Marie Curie, Paris
Sept. 21 to Oct. 15, 1997 (REHE No. 23-97)
The visitor worked in Paris from September 21 to October 15, 1997
The purpose of this visit was to discuss the possibilities of including an
explicit treatment of non-dynamic correlation within a relativistic framework
in the BDF (Beijing 4-component density functional) code.
Two possible ways were taken into consideration. The first one is to use
information which is easily provided by density functional codes, like the
procedures proposed by Ziegler or by Becke, Savin and Stoll.
The second approach needs explicit evaluation of two-electron integrals.
(Their replacement by density functional expressions, along the lines
proposed by Ziegler or by Savin, Stoll and Preuss was also discussed.)
While exploratory atomic calculations were already performed during the visit,
the computation of new integrals needs a more serious modification of the BDF
code and will be pursued in future.
++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++
================================================================================
--- 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 Martin Kaupp]
Conference announcement/reminder (update March 1998):
----------------------------------------------------------------------------
CONFERENCE ON
"Quantum Chemical Calculations of NMR and EPR Parameters"
Bratislava (castle Smolenice), Slovakia,
on 14 - 18 September, 1998.
----------------------------------------------------------------------------
Major Topics Include:
---------------------
Quantum chemical studies of nuclear shielding tensors, spin-spin coupling,
nuclear quadrupole coupling, hyperfine coupling, electronic g-tensors
List of speakers (up to now):
------------------------------------------
V. Barone (Napoli, Italy)
R. J. Bartlett (Gainesville,USA)
M. Buehl (Zuerich,Switzerland)
D. M. Chipman (Notre Dame,USA)
S. Colwell (Cambridge,UK)
H. Ebert (Muenchen, Germany)
B. Engels (Bonn,Germany)
L. A. Eriksson (Stockholm, Sweden)
R. R. Ernst (Zuerich,Switzerland)
J. C. Facelli (Salt Lake City,USA)
U. Fleischer (Bochum, Germany)
J. Gauss (Mainz,Germany)
C. J. Jameson (Chicago,USA)
S. Karna (USAF,USA)
P. Lazzeretti (Modena, Italy)
G. H. Lushington (Columbus, USA)
F. Mauri (Lausanne, Switzerland)
P. Pulay (Fayetteville,USA)
W. T. Raynes (Sheffield, UK)
K. Ruud (Oslo,Norway)
D. R. Salahub (Montreal, Canada)
N. M. Sergeyev (Moscow, Russia)
E. van Lenthe (Amsterdam, The Netherlands)
L. Visscher (Amsterdam, The Netherlands)
P. von R. Schleyer (Erlangen,Germany)
K. Schwarz (Wien, Austria)
R. E. Wasylishen (Halifax,Canada)
J. Weber (Geneva,Switzerland)
T. Ziegler (Calgary,Canada)
------------------------------------------
Organizing Committee
--------------------
V.G. Malkin (Bratislava,Slovakia) (Chair)
M. Kaupp (Stuttgart,Germany)
International Scientific Committee
------------------------------------
W. Kutzelnigg (Bochum,Germany)
J. Oddershede (Odense,Denmark)
P. Pyykko (Helsinki,Finland)
W.T. Raynes (Sheffield,UK)
J.A. Tossell (Maryland,USA)
----------------------------------------------------------------------------
More information with continuous updates, as well as preliminary registration
forms are available on the conference web pages:
http://www.theochem.uni-stuttgart.de/~mkaupp/smolen.html
http://www.savba.sk/sav/inst/uach/smolen.html
To receive the official second circular (probably in April 1998),
preliminary registration should be completed by e-mail to NMR98@savba.sk
or by regular mail to:
NMR-EPR-98
Institute of Inorganic Chemistry
Slovak Academy of Sciences
Dubravska Cesta 9
SK-84236 Bratislava
Slovak Republic
----------------------------------------------------------------------------
NMR-EPR-98 Conference, Bratislava
PRELIMINARY REGISTRATION FORM
Name:.................................................................
.....................(First Initial Last ); Title:....................
Institution:..........................................................
......................................................................
Address:..............................................................
......................................................................
......................................................................
......................................................................
Country:..............................................................
......................................................................
Phone:................................................................
......................................................................
FAX:..................................................................
Email:................................................................
Scientific contribution (tentative title):............................
......................................................................
############################################################################
++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++
[communicated by Jacek Karwowski]
REHE WORKSHOP ON SPIN-ORBIT COUPLING IN CHEMICAL REACTIONS
Institute of Physics, Nicholas Copernicus University, Torun, Poland
January 24 -- 27, 1998
The workshop was held at the Institute of Physics of the Nicholas Copernicus
University in Torun. It was concerned not only with theoretical methods and
computational details, but also with qualitative findings of SOC
manifestations in spectra and reactivity of molecules. The conceptual
importance of SOC effects in chemistry has been emphasized in many
contributions.
There were 18 oral contributions and 18 posters presented during the
meeting. All contributions discussed various aspects of relativistic effects
in atoms and in molecules. About 60% of them were concerned with
spin-orbit-coupling-related phenomena. The remaining ones addressed various
aspects of relativistic theory of atoms and molecules ranging form formal
considerations on Dirac-Coulomb Sturmians to presentations of results of
specific calculations. Since the meeting was intended to be partly a school,
there were several tutorial talks and the research talks contained rather
broad tutorial introductions.
One of the aims of the meeting was to create of an opportunity for an
exchange of ideas between scientists from the Western Europe and their
colleagues from the former Soviet Union Countries. There were 40 scientists
participating in the meeting. Out of them 9 came from the former Soviet
Union (Estonia, Latvia, Russsia, Ukraine), 22 from the Central Europe (Czech
Republik, Poland, Slovakia) and 9 from the Western Europe (Belgium, Finland,
France, Germany, Sweden).
The total budget of the workshop was 40 000.- FRF. A financial support has
been given to all participants from the former Soviet Union, from the Czech
Republic, from Slovakia and to the invited speakers (all together to 20
participants).
Jacek Karwowski
---------------------------------------------------------------------------------
LIST OF PARTICIPANTS
Maria Barysz Torun, Poland teomjb@chem.uni.torun.pl
Eugeniusz Bednarz Torun, Poland eugeneb@phys.uni.torun.pl
Dorota Bielinska-Waz Torun, Poland dsnake@phys.uni.torun.pl
Miroslaw Bylicki Torun, Poland mirekb@phys.uni.torun.pl
Elena Chomenko Cherkassy, Ukraine akin@bee-pitron,cherkassy.ua
Ruvin Ferber Riga, Latvia ferber@acad.latnet.lv
Alexander Glushkov Odessa, Ukraine synop@ogmi.odessa.ua
Wlodzimierz Jaskolski Torun, Poland wj@phys.uni.torun.pl
Jacek Karwowski Torun, Poland jka@phys.uni.torun.pl
Vladimir Kelloe Bratislava, Slovakia kelloe@nic.fns.uniba.sk
Jacek Kobus Torun, Poland jkob@phys.uni.torun.pl
Konrad Koc Krakow, Poland sfkoc@cyf-kr.edu.pl
Roman Kozlowski Olsztyn, Poland kozrom@tufi.wsp.olsztyn.pl
Marek Krosnicki Gdansk, Poland kro@disneyland.mif.pg.gda.pl
Sven Kruger Muenchen, Germany krueger@theochem.tu-muenchen.de
Dorota Kulaga Krakow, Poland dorota@dekan.wsp.krakow.pl
Svetlana Malinovskaya Odessa, Ukraine synop@ogmi.odessa.ua
Uko Maran Tartu, Estonia uko@chem.ut.ee
Christel Marian Bonn, Germany cm@sfb334.thch.uni-bonn.de
Laurent Maron Toulouse, France tei@irsamc1.ups-tlse.fr
Jan Micanko Bratislava, Slovakia micanko@theochem.chtf.stuba.sk
Boris Minaev Cherkassy, Ukraine boris@ifm.liu.se
Valentina Minaeva Cherkassy, Ukraine
Jan Najbar Krakow, Poland najbar@trurl.ch.uj.edu.pl
Elena Pazyuk Moscow, Russia elena@laser.chem.msu.su
Grzegorz Pestka Torun, Poland gp@phys.uni.torun.pl
Pekka Pyykkoe Helsinki, Finland pekka.pyykko@helsinki.fi
Carl Ribbing Leuven, Belgium carl.ribbing@chem.kuleuven.ac.be
Szczepan Roszak Wroclaw, Poland roszak@kchf.ch.pwr.wroc.pl
Andrzej Rutkowski Olsztyn, Poland andrut@tufi.wsp.olsztyn.pl
Andrzej Sadlej Torun, Poland teoajs@chem.uni.torun.pl
Bernd Schimmelpfennig Stockholm, Sweden bernds@physto.se
Jozef Sienkiewicz Gdansk, Poland jes@mif.pg.gda.pl
Monika Stanke Torun, Poland samuel@phys.uni.torun.pl
Andrey Stolaryov Moscow, Russia avstol@laser.chem.msu.su
Michal Straka Brno, Czech Republik straka@cis.vutbr.cz
Radek Szmytkowski Gdansk, Poland radek@mifgate.mif.pg.gda.pl
Christian Teichteil Toulouse, France tei@irsamc1.ups-tlse.fr
Juha Vaara Oulu, Finland jvaara@sun3.oulu.fi
Joachim Werner Stuttgart, Germany werner@theochem.uni-stuttgart.de
------------------------------------------------------
LECTURES;
M. Barysz (Torun): Relativity by perturbation theory: Effects of
inacuracies in the reference function
R. Ferber (Riga): Spin-orbit coupling effects in spectra of Te2 molecule.
J. Karwowski (Torun): Introduction to the relativistic theory of
many-electron systems.
V. Kelloe (Bratislava): Electron correlation and relativistic effects in
calculations of electric properties of atoms and molecules
C. Marian (Bonn): The performance of the spin-orbit mean-field approximation
in molecular calculations
L. Maron (Toulouse): The mean-field SO-method with ECPs
B. F. Minaev (Cherkassy and Link"oping):
The role of one-center spin-orbit coupling model in organic chemical reactions
B. F. Minaev (Cherkassy and Link"oping):
Spin-orbit coupling effects in NMR, ESR and UV molecular spectroscopy
J. Najbar (Krakow): Heavy atom effects in the relaxation of excited aromatic
molecules in rigid and fluid systems
P. Pyykkoe (Helsinki): Relativistic effects in the chemistry of heavy elements.
C. Ribbing (Leuven): SOC in 3d element photochemistry.
S. Roszak (Wrocl{}aw): Spin-Orbit Configuration Interaction Study of the
Electronic Spectrum of IO
A. Rutkowski (Olsztyn): Direct perturbation theory for strongly interacting
molecular states
A. Sadlej (Torun): Two-component approximations in relativistic theories.
B. Schimmelpfennig (Stockholm): The mean-field SO-method: Theory and
applications
J. Sienkiewicz (Gdansk): Spin-orbit interaction in electron-heavy atom
collisions".
R. Szmytkowski (Gdansk): The Dirac-Coulomb Sturmian functions
H.-J. Werner (Stuttgart): Ab initio study of SOC effects in molecular
spectra and reaction dynamics.
____________________________________________________________________________________________
POSTERS:
(in parentheses are names of the coauthors who do not participate in the meeting)
A. V. Glushkov
Relativistic density-functional theory based on quantum
electrodynamics for multielectron systems
A. V. Glushkov (with S. V. Ambrosov, T. V. Buyadgi, A. V. Efimov)
SOC effects in spectra of Rydberg resonances for heavy elements in
electric field
A.V.Glushkov (with A.F.Kivganov and V.A.Efimov)
Heavy elements, relativistic-soc effects in catalysis processes
A.V.Glushkov (with Yu.A.Kruglyak, V.D.Parkhomenko, P.N.Tcybulev,
A.S.Katashinsky)
Relativistic DFT calculations of heavy elements clusters
A.V.Glushkov, S.V.Malinovskaya (with I.Shpinarev and S.Danko)
Spin-orbit effects in electron satellites spectra
production in intense laser field on nuclei in atom,
ion and molecule: relativistic and QED approaches
A.V.Glushkov, S.V.Malinovskaya (with L.A.Vitovetskaya)
Ground and excited states of alkali dimers: potential curves
with spin-orbit coupling
G. I. Kobzev and B. F. Minaev
Collision-induced singlet-triplet transitions in molecular oxygen
K. Koc (with M. J. Vilkas and Y. Ishikawa)
Quadratically convergent multiconfiguration Dirac-Fock and multireference
relativistic configuration interaction calculations for many-electron
systems
R. Kozlowski and A. Rutkowski
Double perturbation approach to the relativistic hydrogenic atom in
magnetic field
D. Kulaga (with J. Migdalek)
Relativistic effects in Ba
S. V. Malinovskaya (with V. N. Polischuk and V. N. Orlova)
Relativistic calculation of Ne-and Ar-like multicharged ions: SOC
effects
L. Maron, B. Schimmelpfennig and Ch. Teichteil (with H. Fagerli,
O. Gropen and U. Wahlgren)
SOC and relativistic effects in transition metal-, actinide- and
gold-compounds
L. Maron, C. Teichteil
Influence of the all-electron relativistic reference atomic calculations
on the SO pseudopotentials splittings
L. Maron, C. Teichteil
A test on the validity of a two-step relativistic method for molecules
containing heavy elements
J. Micanko (with S. Biskupic)
Systematic generation of generally contracted relativistic Gaussiam
basis sets
V. A. Minaeva, B. F. Minaev (with O. Homenko)
Spin-orbit coupling effects in ozone synthesis and photodissociation.
M. Straka and V. Kell"o
Model compounds of borane with Zn, Cd, and Hg. Correlated Douglas-Kroll
calculations.
J. Vaara (with K. Ruud, O. Vahtras, H. AA gren, and J. Jokisaari
MCSCF quadratic response calculation of the electronic spin-orbit
contribution to nuclear shielding tensors
-------------------------------------------------------------------------------
ABSTRACTS:
ORAL CONTRIBUTIONS
------------------------------------------------------------------------------
Relativity by perturbation theory: Effects of inacuracies in the
reference function
Maria Barysz
Department of Quantum Chemistry, Faculty of Chemistry,
N. Copernicus University, Gagarina 7, PL-87 100 Torun, Poland
The first order relativistic corrections to energies can be determined
either from the direct perturbation expansion of the Dirac equation or by
using the so-called Pauli operator. The two formulae are equivalent for the
exact non-relativistic reference functions but lead to different results for
approximate solutions. The analysis of a model problem with controlled
deviation from the exact non-relativistic solution clearly shows a
preference for the first-order relativistic energy formula derived from
direct perturbation theory. The use of the Pauli approximation with
inaccurate non-relativistic reference functions may introduce significant
inaccuracies in the calculated relativistic corrections for low-lying
s-states.
--------------------------------------------------------------------------------
Spin-Orbit Coupling Effects in the Spectra of Te_2 Molecules
R. Ferber
Department of Physics, University of Latvia, Riga LV-1586, Latvia
The Te_2 molecule is a convenient test object of a heavy dimer, free of
hyperfine structure for an even isotope and possessing a Hunds case (c)
coupling scheme because of strong spin-orbit interaction. A complex
experimental study of such Te_2 characteristics as energetic (term values,
level shifts), radiative (lifetimes, relative intensities in laser induced
fluorescence), magnetic (values and signs of Lande factors, magnetic field
induced alignment-orientation conversion, magnetic predissociation) have
been used, in the unified approach, for deperturbation treatment, as well as
to determine the power and type of intramolecular interactions, in
particular, spin-orbit (SO) coupling effects. The main semiempirical
approach in evaluating the SO coupling parameters is based upon empiric
fitting procedure in expanding (c) -- case wavefunctions over (a) -- case
basis. The following particular examples are considered. The measured Lande
factor value allowed to clarify that the thoroughly studies 1_{u state of rm
Te_{2 is an admixture of 86% B, 3Sigma-_{1 and 14% A, 3Pi_{1 states mixed by
SO coupling. The measured ratios of parallel electric dipole transition
moments allow to evaluate the ratios of respective SO mixing constants. The
measured spin-forbidden B, 3Sigma-_{u - b, 1Sigma+_{g transition dipole
moment allows to pass to X, 3Sigma-_{g sim b , 1Sigma+_{g SO mixing
constant. In all cases experimental and semiempirically estimated SO
parameters, based on leading electronic configuration, are compared.
Finally, experimental B, 1_{u state lifetimes are analysed in order to
evaluate the SO effect caused predissociation reaction rate.
[1] E. A. Pazyuk, A. V. Stolyarov, M. Ya. Tamanis, and R. S. Ferber, J.
Chem. Phys. 99, 7873 (1993)
[2] M. Auzinsh, A. V. Stolyarov, M. Tamanis, and R. Ferber, J. Chem. Phys.
105, 37 (1996)
------------------------------------------------------------------------------
Introduction to the relativistic theory of many-electron systems
J. Karwowski
Instytut Fizyki, Uniwersytet Mikolaja Kopernika, Torun,
ul. Grudzic{adzka 5, 87-100 Torun, Poland
A brief introduction to the relativistic theory of atoms and molecules is
given. In particular, the Dirac equation for a single particle, its general
properties, a transition to the nonrelativistic limit and generalizations of
the formalism to the many-electron case are presented. Computational
cosequences of the unboundensss from below of the Dirac spectrum and of
singularities of the Pauli operator are discussed. The origin of the
spin-orbit interaction and its influence on spectra and on other atomic and
molecular properties are briefly analyzed.
-------------------------------------------------------------------------------
Electron correlation and relativistic effects in calculations of electric
properties of atoms and molecules
Vladimir Kelloe
Department of Physical Chemistry, Comenius University,
SK-84215 Bratislava, Slovakia
In the talk will be presented and analyzed results of calculations of
electric properties of atoms and molecules. Electron correlation effects
were accounted for at different levels of the approximation, varied from the
simplest MBPT2 one up to the sophisticated Coupled Cluster methods with
singly, doubly, and triply (noniterative or iterative) excitations included.
Relativistic effects were treated within the Mass-Velocity-Darwin (MVD) or
Douglas-Kroll (DK) schemes. The calculations were focused on heavy atoms
with the atomic number up to 87 and small molecules formed by these heavy
atoms. Dipole moments, dipole polarizabilities, ionization potentials and
electron affinities results will be presented. A special part will be be
dedicated to "molecular" calculations of nuclear quadrupole moments.
---------------------------------------------------------------------------
On the Performance of the Spin-Orbit Mean-Field Approximation in Molecular
Calculations
Christel Marian
GMD - National Research Center for Information Technology,
St. Augustin, and Theoretical Chemistry, University of Bonn, Germany
It is shown that the recently developed spin-orbit mean-field Hamiltonian
[1] yields reliable results for heavy element compounds and for light
mole-cules. For the transition metal compounds Pd_2, PdCl, and PtH a further
simplification, i.e. neglecting the multi-center contributions to the
spin-orbit coupling matrix element, can be applied without loss. In these
cases it is possible to transfer the mean-field integrals to a molecular
orbital basis from an effective core potential calculation [2]. This is not
necessarily true for light molecules, where the percentage error of the
one-center approximation can be considerable. For the twist and
syn-pyramidalization modes of ethene contributions of one-center
one-electron and two-electron terms are found to cancel only partially,
depending on the C--C bond distance [3].
[1] B. A. He{ss, C. M. Marian, U. Wahlgren, O. Gropen, Chem. Phys. Letters
251 (1996) 365
[2] C. M. Marian, U. Wahlgren, Chem. Phys. Letters 251 (1996) 357
[3] D. Danovich, C. M. Marian, T. Neuheuser, S. D. Peyerimhoff, and S.
Shaik, JPC A, submitted
----------------------------------------------------------------------------
The Mean-Field SO-method with ECPs
Laurent Maron1, Christian Teichteil1, Bernd Schimmelpfennig2, Ulf
Wahlgren2, Hilde Fagerli3 and Odd Gropen3
1I.R.S.A.M.C, Universite Paul Sabatier, 31062 Toulouse Cedex, France;
2Institute of Physics, University of Stockholm Stockholm, Sweden; 3Institute
of Mathematical and Physical Sciences, University of Tromso, N-9037 Tromso,
Norway
Due to the arbitrary definition of the inner part of the nodeless orbital,
solutions of the ECP calculations, the problem of the SO calculation had
been solved by introducing a pseudo- operator acting on those nodeless
orbital (pseudoorbital). We define a new way of extracting pseudopotentials
from multiconfigurationnals 4-component calculations and we generalize the
use of iterated natural orbital for the SO calculations. We present
spectroscopic results on halogen atoms and molecules in very good agreement
with experiment. Another solution, we propose, is to transfer the So
integrals directly from a all-electron mean-field calculation to an ECP one.
Even though the AE and ECP basis set are rather different, we define a one
to one correspondence of the SO integrals.
---------------------------------------------------------------------------
The role of one-center spin-orbit coupling model in organic chemical
reactions
Boris F. Minaev
Institute of Physics and Measurement Technology
University of Link"oping, S-58183, Link"oping, Sweden
Spin-orbit coupling (SOC) at the intermediate stages of reactions determines
chemical routes of many thermal and photo-processes through the control of
nonadiabatic single t-triplet (S-T) transition probability. The S-T crossing
normally occures at the intermadiate biradicaloid geometry and SOC has often
been analysed by qualitative consideration of the two-centre SOC integrals
in such biradicaloids. The shortcomings of this approach are briefly
discussed here. The role of the one-centre SOC model, well known from
molecular spectroscopy, is stressed and illustrated by few typical examples
of bitopic reactions of oxygen containing molecules. SOC in the cleaved
oxirane biradical is used as a simple introductory example, which is already
studied by ab initio calculation. Previously analysed dioxetane thermolysis
and the Paterno-B{"uchi photoreaction are accomplished here by some new
details. Interpretations of the S-T transitions by the one centre SOC model
are presented here for the O(3P) atom addition to aromatic substances, for
photoisomerization of furans a nd of cyclohexa-2,5-dienones, and for the
alpha-cleavage of carbonyl compounds. Analysis of the S-T potential energy
surfaces crossings obtained by quantum chemical calculations and by
correlation diagrams is generalized and augmented by vibronic perturbation
for some reactions. It is shown that vibronic perturbation is important for
SOC analysis in acyl-alkyl biradicals.
---------------------------------------------------------------------------------
Spin-orbit coupling effects in NMR, ESR and UV molecular spectroscopy
Boris F. Minaev
Cherkassy Engineering and Technological Institute, 257006, Cherkassy, Ukraine
Spin-orbit coupling (SOC) is one of the most important intrinsic magnetic
perturbations in molecules and its role in phosphorescence and in ESR
spectra is well known fo r a long time. Development of response theory for
MC SCF formalism stimulated a great progress in ab initio studies of the
singlet-triplet transitions probability and g-factor calculations in ESR
spectra. The importance of SOC for NMR spectra of heavy elements have been
recognized many years ago and studies of SOC contribution to NMR chemical
shift by modern ab initio techiques is getting popular just recently.
The proposed talk is devoted to calculation of SOC effects in NMR, ESR and
optical spectra on the ground of response MC SCF formalism and includes the
following:
1. Calculations of nuclear magnetic shielding parameters in the ground
singlet and in the trip let excited states, the singlet-triplet (S-T)
transitions probabilty, electronic and nuclear spin-rotational coupling
constants, hiperfine coupling and g-tensors in the triplet state.
Simultaneous calculations of all these SOC-depending properties (together
with nuclear quadrupole resonance parameters in the S and T states) at th e
same level of accuracy (the same basis set, CAS) permit us to make a proper
assignments in interpretation of spectra. At the same time this help to
understand connections between NMR, ESR, (NQR) and optical properties of
molecules.
2. Calculations of the internuclear distance dependence for all these
spin-dependant parameters and assignment of vibrational state dependence.
3. The following molecules will be considered:
a. H_2O, H_2S, H_2Se.
b. HOCl, HOBr, HOJ.
c. HF, HCl, HBr, HJ; FCl, FBr
d. O_2, S_2, Se_2, Te_2, SO, SeO, TeO, SSe, SeTe
e. OCl, OBr, OI, OCl-, OBr-, OI-.
f. O_3, NO_2-.
g. H_2C=O, H_2C=S, H_2C=Se.
i. Pyrazin.
4. The following results are discussed:
(3.a.) In a series of molecules H_2X (3.a) a large deviation in NMR
chemical shift (delta_ H) have been observed for X = Se. Preliminary
semiempirical calculations have shown that it could be explained by SOC
account. Large scale ab initio calculations are necessary for a proper
explanation of this trend. At the same time the internuclear distance
dependence of the delta_H chemical shift is predicted, since the triplet
excited state of the molecule H_2X is getting the ground state in the
dissociation limit H_2 + X(3 P). Calculations of SOC matrix elements
along the reaction coordinate help us to understand photodissociation
dynamics and to predict the triplet state properties of these molecules
including the T-S transition intensity.
(3.b.) Calculation of the S-T transition probability in these series is
important for atmospheric photochemistry, since it can explain a new path
of production of very reactive radicals OH + Br, I.
(3.c.-e.) SOC calculations in these series has fundamental importance for
many branchs of modern spectroscopy and photodissociaton dynamics.
Connections with NMR and ESR parameters perform new criteria of
spectroscopic assignments which could be equally important in optical and in
radiofrequency regions.
(3.f.) Triplet states of nitrite ion are well studied by optical detection
of magnetic resonance (ODMR) and by ENDOR techniques. The old calculations
of the hyper-fine interaction (HFI) tensor and g-tensors toge ther with
radiative lifetime of the triplet state spin-sublevels were proving very
usefull for ODMR assignment. The ENDOR measurements provides very rich
information about fine, hyper-fine and NQR staructure of the lowest T state.
It is interesting to perform new ab initio calculations of all these
parameters of spin-hamiltonian and compare them with the ground state NMR
and NQR properties. The S-T transition intensity provides an additional
important criterion of the accuracy of SOC account. For isoelectronic ozone
molecule the lowest triplet state (3A_2) has two minima on potential
energy surface. The prediction of the S-T transitions probability
has been latter supported by many experimental techniques. These findings
raise a number of questions about
the triplet ozone species in the atmosphere: is it formed and if so, how?
What is its concentration? Can it be detected? Does it react with other
species? In adressing these questions we are going to perform claculations
of all spin-hamiltonian parameters for the low-lying triplet states of ozone
3A_2, 3B_2 and 3B_1 and also chemical reactivity of these states
which expected to be the SOC dependent.
(3.g.-i.) Studies of SOC effects in these molecules have general importance
for molecular spec troscopy.
5. Internal and external heavy atom effects in NMR spectra of the ground
state molecule, in ESR and in optical spectra (including optical detection
of magnetic resonance) of the triplet excited state molecules are studied
simultaneously. 6. Discovery of "spin-current" nature of molecular oxygen
magnetic phosphorescence (the b1Sigma_g+- X3Sigma_g- transition or the
atmospheric A oxygen band) made in the framework of semiempirical approach,
has been completely supported later by sophisticated ab initio methods. The
main idea of this approach is proven very useful in explanation and
predictions of solvent induced intensity in oxygen spectra and in spin
dependent oxygen reactivity. The lowest excited a1Delta_g state is highly
metastable; its radiative lifetime at zero pressure limit is more than one
hour. The probability of the a - X transition is determined by the
electronic orbital angular momentum contribution to magnetic dipole
transition moment and is extremely sensitive to collisions. The radiative
lifetime of the a1Delta_g state diminishes by 3--4 orders of magnitude upon
collisions in solvents and in the dense gases. An observed lifetime of the
a1Delta_g state is mainly determined by non-radiative quenchin g in
solvents. Nevertheless the singlet a1Delta_ g state oxygen emission is the
main direct tool for monitoring this important metastable and chemically
active intermediate. The a1Delta_g state, now often referred to as ``singlet
oxygen, has been shown to be important in many applications, and
particularly in biochemistry, including the mechanisms of certain human
diseases, cell aging and laser cancer treatment. Photosensitized oxidation
plays an important role in oxidative damage because natural cells
constituents such as porphyrins or flavins can act as sensitizers. The
research in this line will be continued in the project, including chemical
activity of higher excited states A3Delta_u, A3Sigma+_u and B3Sigma-_u.
These efforts in the project will be united with ozon photochemistry studies
with account of SOC effect. Study of new spin-forbidden channels of ozon
formation and degradation would be important for atmospheric chemistry and
for environment sciences. Some intermediates produced by atomic and
molecular oxygen reactions with unsaturated hydrocarbons and with radicals
will be studied. So the project is devoted mainly to spin-orbit coupling
effects in NMR spectra of heavy molecu les, in ESR spectra of radicals and
triplet state excited species. Some applications to ozone depletion
mechanisms and to other processes in atmosphere photochemistry are expected.
---------------------------------------------------------------------------------
Heavy atom effects in the relaxation of excited aromatic molecules in
rigid and fluid systems
Jan Najbar
Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow, Poland
Relaxations of the excited states of aromatic molecules in solutions
containing heavy atoms involve many different configurations of the
flourophore and the perturbing molecules [1]. The lattice models of binary
or multicomponent solutions and the binomial or multinomial distribution
functions represent very effective tools allowing for averaging various
photophysical quantities. The application of the generalized multinomial
distribution functions for the derivation of the decay functions of the
populations of the excited states of aromatic molecules and the decay
functions of the luminescence are discussed. The approach can be applied to
the description of the transient kinetics in a variety of situations. They
include systems having different geometrical dimensions and structures
(surfaces, zeolites, micellar systems and homogeneous fluid solutions). The
diffusion limitations for the relaxation multilevel systems in the presence
heavy atoms and electron transfer processes originating from initially
excited states are considered. Possible generalizations of
Wilkinson-Medinger equation for rigid and fluid solutions are also
considered.
The rare gas matrices (Ar, Kr, Xe) are very convenient systems for the study
of the external heavy atom effect on the photophysical processes in organic
molecules [2]. The phosphorescence spectra of naphthalene-h8 and -d8
molecules isolated in rare gas matrices show multiple sites with different
couplings between aromatic molecule and rare gas matrix. Apart from spectral
shifts an anisotropy of the spin-orbit-coupling for the phosphorescence
decays of benzene--Kr in mixed Ar--Kr matrices are observed. The positional
dependencies of the relaxation constants of the triplet states of chloro-
and bromoquinolines show the contributions due to the vibronic couplings,
the energy gap dependencies and the spin-orbit couplings. The correlation
between the decay rate constants of the triplet states and the results of
INDO calculations seem to indicate the importance of the charge transfer
states for the internal heavy atom effects in halogeno substituted aromatic
compounds [3]. The decays of the singlet and triplet states of aromatic
compounds in the presence of halide ions (Br--, I- or CNS-) show different
enhancements of the radiative and nonradiative transitions [1,4]. The
external heavy atom effects in these systems involve additional electron
transfer processes originating from the singlet excited states [5,6].[4pt]
[1] J. Najbar, J. B. Birks, T. D. S. Hamilton, Chem. Phys. 23 (1977) 281
[2] J. Najbar, A. M. Turek, T. D. S. Hamilton, J. Lumin. 26 (1982) 281
[3] W. Jarzc{eba, J. Najbar, J. Cioslowski, J. Mol. Struct. 141 (1986) 469
[4] J. Najbar, M.Mac, J. Chem. Soc. Faraday Trans. 87 (1991) 1523
[5] J. Najbar, M. Boczar, A. M. Turek, Chem. Phys. 167 (1992) 37
[6] M. Mac, J. Najbar, J. Wirz, J. Photochem. Photobiol. A: Chem. 88 (1995) 93
-------------------------------------------------------------------------------
Relativistic effects in the chemistry of heavy elements
P. Pyykkoe (Helsinki)
-------------------------------------------------------------------------------
SOC in 3d element photochemistry
C. Ribbing (Leuven)
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Spin-Orbit Configuration Interaction Study of the Potential Energy Curves of IO
S. Roszak
Institute of Physical and Theoretical Chemistry, Wroclaw University of Technology,
Wyb. Wyspianskiego 27, 50-370 Wroclaw, Poland
Neutral IO is formed in the reaction of iodine with ozone, resulting in the
destruction of ozone in the troposphere. Because of that the kinetics and
mechanisms of reactions involving IO are studied by a number of
laboratories. The calculations of the potential energy curves of IO are
performed in three steps. The SCF calculation for IO+ produces molecular
orbitals which are used in the standard multireference single and
double-excitation CI method. The final step in the present method is to
employ nonrelativistic eigenfunctions as basis for the final spin-orbit
calculations. The electronic states corresponding to I(2P_u) and O(3P_g) at
the dissociation limit have been considered.
-----------------------------------------------------------------------------------
Direct perturbation theory for strongly interacting molecular states
A. Rutkowski
Institute of Mathematics and Physics, Pedagogical University,
ul. .Zol nierska 14, PL-10561 Olsztyn, Poland
Direct Perturbation Theory (DPT) for relativistic effects is generalized to
the case of a set of near-degenerate strongly interacting states. This
situation, where the standard approach breaks down, is quite common in atoms
and especially in molecules. DPT consist of a partitioning of the Dirac
equation into a four-component part equivalent to the Sch"odinger equation
and a perturbation [A. Rutkowski, J. Phys. B bf 19, 149, 3431, 3443 (1986);
W. Kutzelnigg, Z. Physik D bf 11, 15 (1989);D bf 15, 27(1990)]. The
partitioning of the Hamiltonian itself is the same as in the perturbation
approach formulated earlier by R.A. Moore [Can. J.Phys. bf 53, 1240, 1247,
1251 (1975)], but DPT contains also a partitioning of the metric, as first
suggested by G.L. Sewell [Proc. Cambridge phil. Soc. bf 45, 631 (1949)] and
later advocated for by Kutzelnigg. Recently [A. Rutkowski and W.H.E.
Schwarz, J. Chem. Phys. bf 104, 8546 (1996)] we have proposed a simple
alternative partitioning of the Dirac Hamiltonian which does not contain a
change of the metric and which is especialy convenient for constructing the
Bloch equation for the Mo ller wave operator Omega. (the final formulas,
however, are independent of path of derivation). An effective
Schr"odinger-like equation within a nonrelativistic model space of
near-degenerate states is derived. The effective Hamiltonian and metric
operators are expressed with the help of a Mo ller wave operator Omega,
which generates the complete four-component Dirac wavefunction from the
nonrelativistic Schr"odinger wavefunction in the finite model space.
Explicit formulae are derived for different orders of h_{eff and s_{eff.
They can be used to determine the relativistic energies to different orders
either directly by diagonalization, or by a perturbation approach. Numerical
results for groups of excited potential curves of the one-electron
quasimolecule Sn99+_{2 and some one-electron two-center model systems are
presented and discused.
---------------------------------------------------------------------------------
Two-component approximations in relativistic theories
A. J. Sadlej
Department of Quantum Chemistry, Faculty of Chemistry,
N. Copernicus University, Gagarina 7, PL-87 100 Torun, Poland
Different ways of reducing the 4-component formalism to that of 2-component
spinors, are considered. The consequences of the 2-component approximations
derived by unitary transform methods are studied. Particular attention is
given to the evaluation of expectation values iand transition properties.
---------------------------------------------------------------------------------
Spin-orbit interaction in electron-heavy atom collisions
J. E. Sienkiewicz
Katedra Fizyki Teoretycznej i Metod Matematycznych Politechnika Gdanska,
80-952 Gdansk, Poland
This lecture is devoted to the manifestation of the spin-orbit interaction
during electron scattering from heavy spinless atoms. The spin-orbit
interaction of the scattered electron in the atomic field is proportional to
the scalar product of the electron-orbital-momentum vector and the
spin-angular-momentum vector of the electron. This scalar product is
positive for electrons with the spin parallel to the orbital momentum and
negative for electrons with spins antiparallel to the orbital momentum. The
scattering potential consists of the Coulomb and the polarization, and the
spin-orbit interaction. Since the last term, namely the spin
orbit-interaction, has different signs for spin-up and spin-down electrons
one gets different scattering potentials. As a consequence, one gets
different scattering cross sections so that one obtains different numbers of
spin-up and spin down electrons in the scattering beams. It means that the
scattered beam is polarized. Several examples are shown. From chemists point
of view it might be interesting that also some studies of spin-dependent
electron scattering from oriented molecules have been already performed.
------------------------------------------------------------------------------
The Dirac-Coulomb Sturmian functions: a tool for relativistic atomic physics
Radoslaw Szmytkowski
Faculty of Applied Physics and Mathematics, Technical University
of Gda{nsk, ul. Gabriela Narutowicza 11/12, PL 80--952 Gda{nsk, Poland
A purpose of the lecture is to popularize the Dirac--Coulomb Sturmian
functions, a powerful tool for relativistic atomic physics introduced
recently by Szmytkowski [1]. In the past, there had been at least two
attempts to construct the Dirac--Coulomb Sturmians [2 - 4] but it was shown
[1] that none of them was successful. In particular, in spite of claims to
the contrary [3, 4], the Oxford L-spinors are not the relativistic
Sturmians.
The Dirac--Coulomb Sturmians generalize the well-known
Schr{"odinger--Coulomb Sturmian functions [5] and are non-trivial solutions
of a Sturm--Liouville problem consisting of a set of coupled first-order
radial Dirac--Coulomb equations augmented by appropriate boundary
conditions. Two kinds of the Sturmian functions are found depending on the
way in which an eigenvalue parameter is chosen. The Sturmians form discrete
functional sets which are complete in the space of two-component spinor
functions. The Sturmians of either kind obey two orthogonality and two
closure relations. They are ideally suited for constructing a discrete
expansion of the Dirac--Coulomb Green function [1].
The Dirac--Coulomb Sturmians may find wide applications in relativistic
atomic physics and in QED. For instance, the Sturmian expansion of the
Dirac--Coulomb Green function may be used in calculations based on the
perturbation theory. This was illustrated by Szmytkowski [1] who derived an
analytical formula for a static electric dipole polarizability of the
relativistic hydrogen-like atom. The Sturmian functions may be also employed
as pseudostates in relativistic electron--atom scattering or photoionization
calculations.
The relativistic Sturmian functions may be used in finite basis set
variational calculations. We shall present results of applications of the
Sturmian basis in the variational determination of energy eigenvalues of the
Dirac--Coulomb Hamiltonian. It appears that the variational spectrum of the
problem has many interesting features, among them it obeys a generalized
Hylleraas--Undheim theorem found earlier for the Slater spinor basis by
Drake and Goldman [6, 2].
[1] R.Szmytkowski, J.Phys.B 30 (1997) 825--61 [Erratum: 30 (1997)
2747]
[2] G.W.F.Drake, S.P.Goldman, Adv.At.Mol.Phys. 25 (1988)
393--416
[3] I.P.Grant, in: ``The Effects of Relativity in Atoms, Molecules,
and the Solid State, edited by S.
hspace*{15ptWilson, I.P.Grant, B.L.Gyorffy (Plenum, New York, 1991)
pp.17--43
[4] I.P.Grant, in: ``Atomic, Molecular, and Optical Physics
Handbook, edited by G.W.F.Drake (AIP,
hspace*{15ptWoodbury, 1996) pp.258--86
[5] M.Rotenberg, Adv.At.Mol.Phys. 6 (1970) 233--68
[6] G.W.F.Drake, S.P.Goldman, Phys.Rev.A 23 (1981) 2093--8
------------------------------------------------------------------------------
Ab initio study of SOC effects in molecular spectra and reaction dynamics
H.-J. Werner (Stuttgart)
------------------------------------------------------------------------------
-------------------------------------------------------------------------------
POSTERS
POSTER 1: Relativistic density-functional theory based on quantum
electrodynamics for multielectron systems
A. V. Glushkov
Dept. Appl. Math. and Lab. At. -Nucl. -Mol. Spectr. ,OHMI,
a/c 108, Odessa-9, 270009, Ukraine
Within quantum electrodynamics (QED) its developed a density-functional
(DF) formalism providing the construction of the optimal one-electron
represantation in the theory of the multielectron systems.We use an energy
approach based on the adiabatic Gell-Mann and Low formula for the energy
shift dE with the QED scattering matrice. It is formulated ab initio
criterion for the choice of the atomic core electron density d for atom
(molecule) with a few quasiparticles above closed shells core. The
optimization criterion for d is reduced to the minimization of the DF which
represents the contribution of main polarization diagrams of the QED
perturbation theory fourth order: A=direct polarization ,B=exchange (for
one-qua- siparticle density system) [1]. These contributions describe
collective effects and are dependent on the electromagnetic potential gauge.
We have calculated the contributions of A & B diagrams into imaginary part
of dE taking into account the exchange of electrons by transverse &
longitudinal photons. Minimization of the DF Im dE leads to integro-
differential equation for d, solved using the standard numerical code [2].
The developed theory is numerically tested by calculation of the electron
structure & spectra for some complex atoms,ions and molecules (Na,Cs,Fr,like
ions, N2,O2,CO2,C6H6 etc.) with account of the core polarization [3].
[1] Glushkov A.V. and Ivanov L.N., Phys.Letters A,170,33 (1992). [2]
Glushkov A.V. and Ivanov L.N., J.Phys.B, 26,N16, L379(1993). [3] Glushkov
A.V. et al, Int.J.Quant.Chem.,(1997).
------------------------------------------------------------------------------------
POSTER 2: SOC effects in spectra of Rydberg resonances for heavy elements in
electric field
A. V. Glushkov1, S. V. Ambrosov1, T. V. Buyadgi1, and A. V. Efimov2
1 Dept. Appl. Math. and Lab. At. -Nucl. -Mol. Spectr., OHMI, a/c 108,
Odessa-9, 270009, Ukraine; 2 Institute of Spectroscopy, Russian Academy of
Sciences (ISAN), SU-142092, Troitzk, Moscow region, RUSSIA
There are presented the results of the theoretical study of the
autoionization resonances (AR)in complex multielectron heavy elements
systems (heavy rare-earth atoms, their oxides) in the external electric and
laser field [1,3]. There have been discovered the unussual especialities of
their behaviour in a field, in particular, an effect of giant broadening of
the AR widths in the weak external field.There are considered 2 main AR
decay channels.One of them is the traditional Beutler-Fano channel.Another
one is a new decay type ( the reorientational decay (RD) [2] ).An
appreciable dependence of the RD velocity at the moderately weak (sim 100
V/cm) electric field has been predicted [1,3]. The SOC effects role has been
found. Detailed information about the AR is needed to optimize excitation
and ionization processes.An optimal scheme presumes the compromise between
the high excitation probability and high decay rate that determines the
lower and upper boundaries for the AR decay rate. The use of the RD channel
essentially increases the possibility of such a compromise. New
possibilities of the optimization for the laser resonance ionization scheme
with account of these effects are indicated (for laser chemistry etc).
[1] Glushkov A.V.,Ivanov L.N. Preprint of ISAN N1,2-AS-94; Troitsk, (1994);
Proc. 5th ASOSALP Conf.,Paris,1995
[2] Vidolova-Angelova E.P.,Ivanov L.N. J.Phys.B.:At.Mol.Opt. Phys.,24,4147
(1991)
[3] Glushkov A.V. et al, Abstr.28th EGAS, Vienna,(1996)
------------------------------------------------------------------------------
POSTER 3: Heavy elements, relativistic-soc effects in catalysis processes
A.V.Glushkov, A.F.Kivganov and V.A.Efimov
Dept. Appl. Math. and Lab. At. -Nucl. -Mol. Spectr., OHMI, a/c 108, Odessa-9,
270009, Ukraine
New relativistic theoretical approach has been developed to descibe the
catalytic & absorption phenomena with the parti- cipance of the heavy
elements. Method is based on the electro- dynamical model and relativistic
quantum-mechanical model with the use of the relativistic Dirac equation. It
generalizes the early proposed non-relativistic method [1-3]. As an
example,we considered the catalytic hydrogen electrooxidation and oxygene
electrorestoring reactions and have shown that the correct des- cription of
the heavy elements catalytic materials properties requires the adequite
account for the relativistic corrections. We also examine an action of the
laser and electric field on catalysis process.Some materials non possesing
by catalytic properties become the catalisators under action of the laser
field & vice versa. Theory of the catalysis in external fields is presented
[4].
[1] A.V.Glushkov, Sov.ElectroChemistry. 27,131 (1991). [2] A.V.Glushkov,
Sov.ElectroChemistry. 29,358 (1993). [3] A.V.Glushkov, Cat.Lett. to be
submitted. [4] A.V.Glushkov, Heavy Elements, Relativistic and Laser Fields
Effects in Catalysis, Moscow-Troitzk, 1996.
-----------------------------------------------------------------------------
POSTER 4: Relativistic DFT calculations of heavy elements clusters
A. V. Glushkov1, Yu. A. Kruglyak1, V. D. Parkhomenko2, P. N. Tcybulev2, A.
S.K atashinsky3
1Dept. Appl. Math. and Lab. At. -Nucl. -Mol. Spectr., OHMI, a/c 108,
Odessa-9, 270009, Ukraine; 2Institute of General and Neorganic Chemistry,
NAN Ukraine, Kiev, Ukraine ; 3Kiev Politechnical Institute, Kiev, Ukraine.
There are presented the results of calculations for the electron
structure, spectra for the lanthanides perovskites (ABO3,A=Ln,Ce; B=Mn,Co),
alkali and heavy elements atoms (Nb, Mo) clusters in neutral form & also
single-, double-charged ones, on the basis of different calculation
methods:density- functional (DF) & relativistic perturbation theory (PT)
with pseudopotential zeroth approximation [1].It has been studied the
contributions of the correlation and relativistic correc- tions into
calculated characteristics, which are to be quite important. This work, in
part,supported by the grant of the Ministry of Science and Technology of
Ukraine, project N 3.4/382.
[1] A.V.Glushkov, E.P.Ivanova, J.Quant.Spectr.Rad.Transfer,36, 127 (1986).
[2] A.V.Glushkov, Int.J.Quant.Chem.(1997),to be submitted.
---------------------------------------------------------------------------
POSTER 5: Spin-orbit effects in electron satellites spectra production in
intense laser field on nuclei in atom, ion and molecule: relativistic and
QED approaches
A. V. Glushkov12, S. V. Malinovskaya3, I. Shpinareva1, S. Dankov1
1 Dept .Appl. Math. and Lab. At. -Nucl. -Mol. Spectr., OHMI, a/c 108,
Odessa-9, 270009, Ukraine; 2 Institute of Spectroscopy, Russian Academy of
Sciences (ISAN), SU-142092, Troitzk, Moscow region, RUSSIA; 3 Odessa Center
of Spectroscopy, a/c 108, Odessa-9,270009
The paper deals with a group of the laser field effects on nuclei in the
neutral atoms,ions & molecules with production of the electron satellites
set in spectra and goes on our work within the following directions in a
laser- electron- nuclear spectroscopy:1).the mixed Y-optical quantum
transitions under intense laser field;2).manifestation ofthe nuclear
properties in the optical spectra and the use of this effect in nuclear
investigations with application of lasers; 3). a drivening by the charged
particles beams papameters by means the laser radiation effect on the
electron shell surrounding the nuclei. Theoretical results of the
calculation of the electron-nuc- lear Y-transition spectra (set of electron
satellites) of the nucleus in a multicharged atomic ion & neutral atom in
presence of the intense field are presented. A mechanism of formation of
the satellites in a case of the ion (rigid electron shell) involves the
direct interaction between Y quantum and atomic electrons.For atom &
molecule (loose shell) the "shaking" of shell resulting from the interaction
between the nucleus & Y- quantum is predominant [1,2]. The relative
intensities of the satellites are calculated within the relativistic version
of the energy approach (S-matrix Gell-Mann and Low formalism) [2]. The
possible satellite observation experiment is in detailes discussed to
provide a search of optimal experiment conditions.
[1] Ivanov L.N. and Letochov V.S. Sov.JETP, 93,396,1987. [2] Glushkov A.V.et
al, Abstr.28th EGAS,Vienna,(1996). [3] Glushkov A.V. and Ivanov L.N.
Phys.Lett.A,70,33,1992; Preprint of ISAN N1-AS-93, Moscow,1993.
---------------------------------------------------------------------------------
POSTER 6: Ground and excited states of alkali dimers: potential curves with
spin-orbit coupling
A.V.Glushkov1, S.V.Malinovskaya2, L.A.Vitovetskaya1
1 Dept. Appl. Math. and Lab. At. -Nucl. -Mol. Spectr., OHMI, a/c 108,
Odessa-9, 270009, Ukraine; 2Center of Spectroscopy, a/c 108, Odessa-9,270009
Within formally exact perturbation theory with model zero approximation
[1-3], it has been carried out the calculation of the potential curves for
the ground and excited states of the homo- and heteronuclear alkali dimers
AB (A,B = K,Cs,Fr) with account of the relativistic effects [3].A
semiempirical model of the Cohen-Schneider type [4], based on the exactly
calculated atomic splittings [5,6] is given for treatment of spin-orbit
coupling effects. There have been predicted some unusual especialitites in
the spectra of the excited states of the heavy alkali diatomics [7]. A part
of the results are obtained at first.
[1] Glushkov A.V. Sov.J.Phys.Chem. 65,N9 (1991); 66,N10 (1992); Sov. J.
Struct. Chem. 34, N5 (1993)
[2] Glushkov A.V. and Ivanov L.N. Phys.Lett.A 70, N1 (1992)
[3] Glushkov A.V. Int.J.Quant.Chem., to be published.
[4] Cohen J.S. and Schneider B. J.Chem.Phys.61,N8 (1974)
[5] Glushkov A.V. Sov.Opticks and Spectroscopy 36,N6 (1994)
[6] Glushkov A.V. Sov.Applied Spectr.Journ.36,N6 (1994);
[7] Glushkov A.V. Phys.Lett.A , to be published.
-------------------------------------------------------------------------
POSTER 7 Collision-induced singlet-triplet transitions in molecular oxygen
G. I. Kobzev1 and B. F. Minaev 2
1Department of Chemistry, Karaganda University, Universitetskaja 28, 470074
Karaganda, Kazakhstan; 2Department of Chemistry, Cherkassy State University,
Cherkassy, Ukraine
Different types of collision complexes between O_2 and diamagnetic species
(H_2, NH_3, ethylene, benzene) have been considered by MINDO/3 CI, MRCI and
MCSCF response (6-31 G*) calculations in order to simulate paramagnetic
spin-catalysis of photophysical and photochemical properties of oxygen
containing organic solvents and mixtures of gases.
-------------------------------------------------------------------------
POSTER 8: Quadratically convergent multiconfiguration Dirac-Fock and
multireference relativistic configuration interaction calculations for
many-electron systems
Marius J. Vilkas1, Yasuyuki Ishikawa1 and Konrad Koc2
1Department of Chemistry and The Chemical Physics Program, University of
Puerto Rico, P.O.Box 23346, San Juan, PR 00931-3346, USA; 2Department of
Physics, Pedagogical University, ul. Podchorazych 2, 30-084, Krakow, Poland
A quadratically convergent Newton-Raphson algorithm for relativistic
multiconfiguration Dirac-Fock self-consistent field calculations is
developed and implemented with analytic basis sets of Gaussian spinors. A
procedure to perform second-order energy optimization for a general class of
multiconfiguration wave functions constructed from one-particle Dirac
spinors is described. We report the results of relativistic
multiconfiguration Dirac-Fock self-consistent field calculations and
relativistic multireference configuration interaction calculations based on
the multiconfiguration Dirac-Fock wave functions for the lowest 3P_0, %
3P_1, and 3P_2 states of oxygenlike iron (Fe+18) and ground-state beryllium
and berylliumlike neon (Ne+6), species which exhibit the near degeneracy
characteristic of a manifold of strongly interacting configurations.
----------------------------------------------------------------------------
POSTER 9: Double perturbation approach to the relativistic hydrogenic atom
in a magnetic field
R Kozlowski and A Rutkowski
Institute of Mathematics and Physics, Pedagogical University, ul. Zolnierska
14, 10-561 Olsztyn, Poland.
Double perturbation theory is developed for the case where relativity is one
perturbation and the second perturbation describes the interaction with
external magnetic field. Relativity is treated according to direct
relativistic perturbation theory developed by Rutkowski [J. Phys. B 19, 149,
3431, 3443 (1986)] and Kutzelnigg [Z. Phys. D. 11, 15, (1989); 15, 27
(1990)].
The relevant radial perturbation equations and formulae for the corrections
for the energy are derived. For the ground state up to the first order in
magnetic field all the differential equations arising are solved directly to
infinite order in relativity. The general solutions of the radial equations
are obtained by expansion in appropriate Laguerre polynomials. Exact energy
corrections for zeroth and first order as well as very accurate results for
second and third order in relativity are presented up to twelve order in
magnetic field.
------------------------------------------------------------------------------
POSTER 10: Relativistic effects in Ba
D.Kulaga, J. Migdalek
Pedagogical University in Cracow, ul. Podchorazych 2, 30-08 Krakow
In order to systematically study the influence of relativistic effects on
energy levels and oscillator strengths in Barium, we used four diffrent
approaches. First we performed calculations using ab-initio
non-relativistic Hartree-Fock (HF) and a pseudorelativistic method (HFR) in
which mass-velocity and Darwin contributions were included to evaluate the
one-electron and the total binding energy. In the second part of
calculations we used a semiempirical fit of Slater intengrals to minimize
discrepancies between observed and computed energy and core polarisation
corrections to the dipole transition matrix element (HF+CP+FIT and
HFR+CP+FIT, respectively). To account for intravalence electron correlation,
CI approach has been used. The basis set for the calculations consist of 13
even and 7 odd configurations. Computations are performed in LS copupling
scheme. As a tool has computer package written by R.D.Cowan of Los Alamos
National Laboratory has been used. The calculated energy levels and the
oscillator strengths between levels under considerations have been compared
with available data.
-----------------------------------------------------------------------------
POSTER 11: Relativistic calculation of Ne-and Ar-like multicharged ions: SOC
effects
S. V. Malinovskaya1, V. N. Polischuk2 and V. N. Orlova2
1Odessa Center of Spectroscopy, a/c 108, Odessa-9,270009; 2Dept. Appl. Math.
and Lab. At. -Nucl. -Mol. Spectr., OHMI, a/c 108, Odessa-9, 270009, Ukraine
Laborotary X-ray investigations supplemented recently with new ideas
concerning resonant photoionization as the pumping mecha- nism.Its known
that the spectral intensity of a pump line would be more than
10(10)w/cm(2)mA.In this case the presence of strong electric microfields
complicates a prediction of spectroscopic characteristics for ions. As
result a comprehensive theoretical model to describe laser enhancement in
plasma ist elaborated yet. Ne - like scheme for lasing represented to be one
of the promising scheme. In this light the precise calculations of the
energies and transition probabilities,excitation cross-sections of a great
impotance. We present the results of the theoretical and experimental
studing the spectra (wavelengths) , transition probabilities of 3-3, 3-4
electron and 2-2 vacancy transitions for Ne-like isoelectronic sequence
(19>> 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
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[see the editorial note on this topic above]
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--- ADDRESS LIST
The REHE address list comprises 195 scientists as of March 24, 1998; the
next address list will be provided with newsletter no. 32
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End of REHE Newsletter No. 29