RELATIVISTIC EFFECTS IN HEAVY-ELEMENT CHEMISTRY AND PHYSICS

EUROCONFERENCE
Relativistic Quantum Chemistry Progress and Prospects,
10-15 April 1999, Acquafredda di Maratea, Italy
(Organisers: J. G. Snijders Groningen, Netherlands, I. P. Grant
Oxford U.K.)
In a paper of 1929, Dirac famously said that relativistic effects are
of

no

importance

in

atomic

and

molecular

structure

and

ordinary chemical reactions, in which it is, indeed, usually sufficiently

accurate if one neglects relativity variation of mass with velocity and
assumes only Coulomb forces between the various electrons and
atomic nuclei. Whilst much of quantum chemistry implicitly continues
to

accept

this

assessment,

the

increasing

sophistication

of

experimental and computational work has encouraged a rapid growth

in the use of relativistic models, since the 1960s in atomic structure
theory and, much more recently, in molecular structure theory and
processes.

Relativistic

quantum

beginning to show signs of

chemistry

maturity,

is

with the

field,

focus

which

is

shifting from

technical developments into evermore demanding applications. The

European Science Foundations Programme, Relativistic effects in
Heavy Element Chemistry and Physics, which held three previous
EuroConferences in 1993, 1995 and 1997, and made possible many
collaborations and exchanges between scientists across Europe has
given a major stimulus to the field. The 1999 EuroConference was
convened

to

present,

review

and

assess

recent

computational

advances in the relativistic treatment of atoms molecules and solids

and

their

application

to

spectroscopy,

and

chemical

bonding

in

compounds containing heavy elements.

The first of the four areas covered concerned applications to the
chemistry

of

heavy

elements,

with

particular

emphasis

on

the

chemistry of gold where relativistic effects are paramount. Amongst

other highlights was a demonstration that similar techniques could
throw light on some structural problems in organometallics containing
nickel,

palladium

or

platinum.

The

second

area

dealt

with

computational methods. So far most of the applications have used

approximate 2-component methods such as Douglas-Kroll or ZORA,
but the more exact 4-component methods based on Diracs equation
show

promise

relativistic
remains

in

to

for

the

origin,

be

done

future.

were
to

Spin-orbit

covered

in

understand

relativistic and correlation

effects in

effects,

the

the

third

which
area.

complicated

complex

are
Much

purely
work

interplay

of

Finally,

all

systems.

theories rest on an understanding of quantum electrodynamics, and

the fourth area covered several aspects in which highly accurate
wave functions are needed, such as Lamb shifts, hyperfine splittings
and

bound

electron

g-factors.

The

importance

of

fully

relativistic

calculations of electronic structure of the radical YbF to experiments

to set limits on the electric dipole moment of a bound electron whose

detection would signal a breakdown of standard electroweak theory
resulting

from

violation

of

parity-

and

time-reversal

symmetries

emphasizes the close links with relativistic quantum chemistry.

Relativistic quantum chemistry has made great progress in the last
few

years,

in

which

European

scientists

have

made

dominant

contribution. The goal of this European Research Conference was to

present, review and discuss recent advances in the computational
methods developed to treat relativistic effects in atoms, molecules
and

solids

as

well

as

the

application

of

these

methods

to

experimental problems in Spectroscopy and in the description of the

chemical bonding in compounds containing Heavy Elements.

The meeting comprised 4 sessions of lectures by invited speakers,

devoted to the following areas:

Relativistic Effects in Heavy Element Chemistry

Relativistic Computational Methods

Relativistic Effects in Spectroscopy

Relativistic

and

Quantum

Electrodynamic

Effects

in

Atomic

Physics

RELATIVISTIC EFFECTS IN HEAVY ELEMENT CHEMISTRY

Several of

the

presentations in

this

session

concentrated

on

the

relativistic effects in the chemistry of gold, both from a theoretical and

an experimental point of view. A great variety of very interesting
novel compounds of potential industrial importance were reviewed by
the

two

experimental

particular

interest

frameworks

and

compounds.

scientists

are

the

who

nanotechnology

The

are

structural

aggregation

of

experts

aspects
made

gold

in

of

this

possible

complexes

field.

Of

supramolecular
by

these

through

various

types of secondary bonding leads to unprecedented self-assembly

patterns, some of which can be rationalised, while others remain
essentially mystery, mainly owing to the delicate balance of various
small effects. The paramount importance of relativistic effects in gold
compounds

has

been

accurate

correlated

systems,

as

particular

in

well
the

abundantly

4-component
as

with

density

demonstrated,
calculations

various

functional

two

of

both

relatively

component

framework

for

with

very
small

methods

larger

in

systems.

During this session it was also convincingly shown that these latter
methods

are

able

to

rationalise

the

structure

of

quite

large

organometallic compounds of Ni, Pd, and Pt, while the structural

variation could be understood from the important relativistic effects in
the heavier moieties. In conclusion we can say that we now have the
tools to tackle these difficult problems, but that much remains to be
done

in

applying

them

to

the

often

large

systems

that

the

experimentalists are considering now.

Another aspect treated during this session was the influence of spinorbit

splitting

on

the

photochemistry

dynamics

of

transitionmetal

carbonyls, where calculations give crucial insight in the mechanisms

of channel selection and photodissociation pathways.
A final aspect treated in this session was the description of relativistic
effects

on

the

chemical

bonds

through

the

Hellmann-Feynman

theorem, emphasising that often two seemingly disparate views of

relativistic bonding can in fact be equivalent. As an aside a very
interesting description of the tragic life of Hellmann as a scientist was
presented,

which

scientists present.

was

particular

educational

for

the

younger

RELATIVISTIC COMPUTATIONAL METHODS

In this session unfortunately the keynote speaker has had to cancel
at the very last moment due to urgent personal reasons, so we did
not have the benefit of a thorough review as we did in all other
sessions.

Nevertheless

the

various

methods

used

to

analyse

relativistic effects were well represented. Both the approximate 2component methods such as Douglas-Kroll and ZORA as well as the
more exact but expensive 4-component methods clearly are reaching
maturity and are at a stage they can be applied more or less routinely
to

chemical

and

spectrosopic

problems.

The

ZORA

method,

originally developed in a Density Functional setting, has now also

been implemented in a

ab initio

context. There were also several

technical advances presented in the calculation of spin-dependent

matrix elements at the Configuration Interaction level. Finally a lot of
progress

has

been

made

to

make

4-component

methods

more

efficient at both the Dirac-Fock and the correlated (Coupled Cluster)

level and they are now sufficiently well developed that quite sizeable
molecules can be treated as this level. The latter was in particularly
illustrated

with

compounds

of

enhanced role.

several

analyses

superheavy

of

the

elements,

expected
where

bonding

relativity

in

the

plays

an

RELATIVISTIC EFFECTS IN SPECTROSCOPY

A recurring theme in this (shorter) session was the effect of spin-orbit
interaction in various spectroscopies treated. The keynote speaker
gave a very lucid account of the current situation with respect to the
calculation of spectroscopic parameters that are influenced by this
interaction.

She

reviewed

in

particular

the

importance

of

jj/LS

coupling versus intermediate coupling schemes, the influence of the

Breit/spin-other-orbit

interaction,

the

importance

of

electron

correlation, the 4 versus 2 component formulations as well as the

influence of frozen core/valence only approximations. Finally there
was a very useful account of the circumstances under which effective
one-electron spin-orbit Hamiltonians break down (particularly in light
systems).
From

the

experimental

side

the

importance

of

relativistic

effects,

again in particular spin-orbit interaction, was highlighted in the field

photoionisation

and

multiphoton

ionisation.

Here

very

often

quantumchemical calculations are indispensable in the interpretation

of the resulting spectra. Such calculations were also presented at
fully relativistic CI level for the interpretation of Auger spectra, as well
as for the analysis of the interplay of correlation and relativity in the
lighter atoms.
Finally it was shown that modern relativistic density functional theory
is

able

relevant

to
to

anisotropic

reliably

determine

Electron

Spin

g-tensors,

various

Resonance

hyperfine

spectroscopic

parameters

spectroscopy,

interaction

tensors

of

such

as

Kramers

doublet open shell molecules as well as nuclear quadrupole coupling

constants, which involve the calculation of electric field gradients.

RELATIVISTIC AND QUANTUM ELECTRODYNAMIC EFFECTS IN

ATOMIC PHYSICS
The keynote speaker in this session gave a very thorough review of
the

current

status

of

the

effects

of

quantumelectrodynamics

especially in highly charged atomic ions, in particular with respect to

the Lamb shifts, hyperfine splittings and bound-electron g-factors.
Detailed comparison with experiment with a view of testing QED in
higher order were presented. There is considerable overlap between
this field of research and relativistic quantum chemistry, which was
the subject of the other sessions, especially since highly accurate
relativistic atomic wave functions are needed in the analysis of these
effects.

Several

of

the

other

contributions

in

this

session

were

therefore devoted to the methods needed to obtain such atomic wave

functions, with methods akin to those used in molecules.

A fascinating mixed theoretical /experimental contribution considered

the possibility of measuring a possible electric dipole moment of a
bound electron, which would indicate an (expected) breakdown of the
standard electroweak

theory, introducing interactions

which

break

both parity and time-reversal symmetries. Very sensitive experiments

to measure this effect in the YbF molecule are being set up. There is
again a close link with relativistic quantum chemistry, since accurate
relativistic

wavefunctions

are

required

in

order

to

interpret

these

experiments as was emphasised in some if the other contributions in

this final session.
The

session

and

the

conference

was

concluded

by

thought

provoking summing up by the vice-chairman.

FINAL ASSESSMENT
The

conference

quantum

once

chemistry

conference
collaboration

of
of

this

again

is

very

sort.

scientist

showed
lively

Most

from

that

and

the

benefits

contributions

different

field

of

relativistic

greatly

resulted

(predominantly

from

from

European)

countries and several more collaborations were being planned even

during the conference itself. It is fair to say that European scientists
continue to play a leading role in this field, which can be attributed to
a large extent to the former REHE program and the continuity of the
regular series of European conferences of which the present one
was a part. We strongly support the continuation of this series on a
two year basis in order to keep stimulating this community, especially
now the methods developed start to have a marked influence on a
large variety of experimental investigations, both in the chemistry and
physics

community.

We

therefore

also

advocate

the

inclusion

of

leading experimental scientists from the relevant experimental fields

in any subsequent conferences of this sort.

ACKNOWLEDGEMENT
The support from the European Commission EuroConference activity
of the Training and Mobility of Researchers (TMR) is acknowledged.

April 1999

Identification:
Scientist in charge:
Address:

ASTROrelaqchem980383/EW/jb
SNIJDERS Jaap G.
Rijksuniversiteit Groningen, Dept. of
Theoretical Chemistry, Material Science
Centre, Nijenborgh 4, 9747 AG Groningen,
The Netherlands

Tel.:
Fax:
E-mail:
Contractor:

(31) 50 363 4861

(31) 50 363 4441
snijders@chem.rug.nl
HENDEKOVIC Josip
EURESCO Conferences, European Science
Foundation, 1 quai Lezay-Marnsia, 67080
Strasbourg cedex, France
Tel. +33 (0)388 76 71 35
Fax. +33 (0) 388 36 69 87
E-Mail: euresco@esf.org

Contract n:

ERBFMMACT 980383

Publications:
www site:
- for events:
- of contractor:
- other relevant:

http://www. theochem.chem.rug.nl

http://www.esf.org/euresco/99/PC99061a.htm
http://www.esf.org/euresco

PROGRAMME OF EVENTS
Event n1:
Relativistic quantum
Chemistry - progress and
prospects

Dates:
10/04/1999-15/04/1999
5 day

Place:
Acquafredda di maratea, Italy.

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