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Fulvio Cacace (1931Ц2003) Structure and Mechanism in Gas-Phase Chemistry and Its Relevance to the Condensed State.

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Fulvio Cacace (1931–2003):
Structure and Mechanism in
Gas-Phase Chemistry and Its
Relevance to the Condensed State
Fulvio Cacace, Professor of General and
Inorganic Chemistry at the Faculty of
Pharmacy of the university “La Sapienza” in Rome (Italy),
died on December 1,
2003 at the age of 72.
Cacace graduated in
chemistry in 1954; in
1956 he became assistant
professor and in 1971
full professor in Rome.
He held this position
until his death. He was
director of the Nuclear
Chemistry Institute of
the Consiglio Nazionale delle Ricerche
(National Research Council, CNR)
from 1968 to 1974, and later president
of its scientific committee. He was the
national coordinator of the strategic
project “Advanced Technologies and
Methodologies for Radiochemistry” of
the CNR. He also carried out research
at the G. Werner Institute of Nuclear
Chemistry in Uppsala (Sweden, 1960),
the Brookhaven National Laboratory
(USA, 1961–62, 1968, 1977, 1980,
(KFA) in J?lich (Germany, 1972,
1979), and the University of California
in Irvine (USA, 1968). In 2002 he was
elected as a member of the prestigious
Academia Nazionale dei Lincei.
Cacace@s research into certain fundamental aspects of chemistry and
their applications had significant multidisciplinary impact. His interests spanned from the chemistry of ions in the
gas phase to nuclear chemistry, inorganic chemistry, and, in recent years,
atmospheric chemistry. His results were
reported in over 250 scientific publications.
His earlier research activities
included the chemical effects of nuclear
transformations, reactions of nucleogenic atoms at high energies, isotopic
exchange reactions, and the synthesis
of isotope-labeled molecules and their
applications as tracers in chemical, biochemical, and clinical studies. His
research interests then switched to the
investigation of the structure, stability,
and reactivity of ions in the gas phase.
In this field he developed and successfully applied the “decay” technique to
the preparation of otherwise inaccessible species, the structural and stereochemical characterization of many ions
in the gas phase, and the study of their
reactivity in different media, thus allowing direct comparison between liquid
and gaseous systems. This technique,
based on the decay of tritium and
other radioactive atoms located in suitable positions in the molecules under
investigation, is an example of Cacace@s
original approach to scientific problems,
which could often not be solved by conventional methods.[1] The use of positron
emitters, such as 11C, 13N, and 18F, paved
the way for the development of positron
emission tomography (PET).
Cacace studied the chemistry of ions
in the gas phase by an integrated
approach based on mass spectrometry
and radiolytic techniques. He studied
particularly important reaction classes,
such as aromatic alkylation and nitration. The combination of theoretical calculations, applicable to isolated species
in the gas phase, with this integrated
approach allowed the interpretation of
results from studies in the condensed
phase, and conferred to ion chemistry a
central role in the interpretation of
chemical reactivity.
Through studies of the structure, stability, and reactivity of inorganic molecules by theoretical calculations and
mass spectrometric techniques, he was
able to detect and characterize different
protomers of nitrous and nitric acid,
evaluate their proton affinities, and construct extended scales for the binding
energy of NO+ and NO2+ with a large
number of nucleophiles.
This research was extended to
atmospheric chemistry and the extensive investigation of the reactivity of
ozone in ionized mixtures containing
several compounds present in the
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/anie.200420086
atmosphere in trace amounts, such as
freons, COS, O2, N2, CO2, and CO. The
results obtained were relevant to the
chemical investigation of the ionization
of the atmosphere by natural (lightning,
coronas of thunderstorm clouds, solar
and radioactive radiation) or anthropogenic phenomena (power-line coronas).
Research focused on two areas central to atmospheric science and modeling led to the discovery and detection
of new neutral and/or charged transient
species that play key roles, for example,
as catalysts or intermediates in terrestrial, planetary, and satellite atmospheres. Through a combination of theoretical and mass spectrometric techniques he discovered new neutral and
exotic species (in particular O4, N4,
new N, C, and S oxides) of great significance for fundamental research and
because of their possible role in the
atmosphere.[2, 3]
Cacace was an excellent teacher,
with a gift for making difficult problems
simple. He was able to transmit to his
students and co-workers his enthusiasm
for and endless curiosity about chemistry. He devoted his whole life to scientific research. He is survived by his
wife Gabriella, son Filippo, and daughter Marina, and will always be remembered by his many students and friends,
who had the privilege of working with
him for many wonderful years.
Fulvio Cacace was a truly exceptional chemist, a devoted teacher, and
also a dear personal friend. He made
major contributions to chemistry, which
will serve as a lasting memory and inspiration for future generations.
George A. Olah
University of Southern California
Los Angeles (USA)
[1] F. Cacace, Science 1990, 250, 392.
[2] F. Cacace, G. de Petris, A. Troiani,
Angew. Chem. 2001, 113, 4186; Angew.
Chem. Int. Ed. 2001, 41, 4062.
[3] F. Cacace, Chem. Eur. J. 2002, 8, 3838
Angew. Chem. Int. Ed. 2004, 43, 1760
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chemistry, cacace, 1931ц2003, structure, mechanism, condensed, fulvic, state, gas, relevance, phase
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