Ett internationellt forskarlag fick nya insikter om de kemiska egenskaperna hos det supertunga grundämnet flerovium – element 114 – vid acceleratoranläggningarna hos GSI Helmholtzzentrum für Schwerionenforschung i Darmstadt. Mätningarna visar att flerovium är den mest flyktiga metallen i det periodiska systemet. Flerovium är alltså det tyngsta grundämnet i det periodiska systemet som har studerats kemiskt.

Med resultaten, publicerade i tidskriften Frontiers in Chemistry , GSI bidrar till studiet av supertunga grundämnens kemi och öppnar nya perspektiv för den internationella anläggningen FAIR (Facility for Antiproton and Ion Research), som för närvarande är under uppbyggnad.

Under ledning av grupper från Darmstadt och Mainz producerades de två längsta livslängda fleroviumisotoperna som för närvarande är kända, flerovium-288 och flerovium-289, med hjälp av acceleratoranläggningarna på GSI/FAIR och undersöktes kemiskt vid TASCA:s experimentuppställning. I det periodiska systemet placeras flerovium under tungmetallblyet.

Emellertid hade tidiga förutsägelser postulerat att relativistiska effekter av den höga laddningen i kärnan av det supertunga elementet på dess valenselektroner skulle leda till ädelgasliknande beteende, medan nyare snarare hade föreslagit ett svagt metalliskt beteende. Två tidigare genomförda kemiexperiment, ett av dem vid GSI i Darmstadt 2009, ledde till motsägelsefulla tolkningar.

Medan de tre atomerna som observerades i det första experimentet användes för att sluta sig till ädelgasliknande beteende, indikerade data som erhölls vid GSI metallisk karaktär baserat på två atomer. De två experimenten kunde inte tydligt fastställa karaktären. De nya resultaten visar att flerovium, som väntat, är inert men kan bilda starkare kemiska bindningar än ädelgaser, om förhållandena är lämpliga. Flerovium är följaktligen den mest flyktiga metallen i det periodiska systemet.

Flerovium är alltså det tyngsta kemiska grundämnet vars karaktär har studerats experimentellt. Med bestämning av de kemiska egenskaperna bekräftar GSI/FAIR sin ledande position inom forskningen av supertunga grundämnen.

"Att utforska gränserna för det periodiska systemet har varit en pelare i forskningsprogrammet vid GSI sedan starten och kommer att vara så på FAIR i framtiden. Det faktum att ett fåtal atomer redan kan användas för att utforska de första grundläggande kemiska egenskaperna, vilket ger en indikation på hur större mängder av dessa ämnen skulle bete sig, är fascinerande och möjlig tack vare den kraftfulla acceleratorn och expertisen i det världsomspännande samarbetet, säger professor Paolo Giubellino, Scientific Managing Director för GSI och FAIR. "Med FAIR tar vi in ​​universum i laboratoriet och utforskar materiens gränser, även för de kemiska elementen."

Sex veckors experiment

Experimenten som utfördes vid GSI/FAIR för att klargöra fleroviums kemiska natur varade totalt i sex veckor. For this purpose, four trillion calcium-48 ions were accelerated to ten percent of the speed of light every second by the GSI linear accelerator UNILAC and fired at a target containing plutonium-244, resulting in the formation of a few flerovium atoms per day.

The formed flerovium atoms recoiled from the target into the gas-filled separator TASCA. In its magnetic field, the formed isotopes, flerovium-288 and flerovium-289, which have lifetimes on the order of a second, were separated from the intense calcium ion beam and from byproducts of the nuclear reaction. They penetrated a thin film, thus entering the chemistry apparatus, where they were stopped in a helium/argon gas mixture.

This gas mixture flushed the atoms into the COMPACT gas chromatography apparatus, where they first came into contact with silicon oxide surfaces. If the bond to silicon oxide was too weak, the atoms were transported further, over gold surfaces—first those kept at room temperature, and then over increasingly colder ones, down to about –160 °C.

The surfaces were deposited as a thin coating on special nuclear radiation detectors, which registered individual atoms by spatially resolved detection of the radioactive decay. Since the decay products undergo further radioactive decay after a short lifetime, each atom leaves a characteristic signature of several events from which the presence of a flerovium atom can unambiguously be inferred.

One atom per week for chemistry

"Thanks to the combination of the TASCA separator, the chemical separation and the detection of the radioactive decays, as well as the technical development of the gas chromatography apparatus since the first experiment, we have succeeded in increasing the efficiency and reducing the time required for the chemical separation to such an extent that we were able to observe one flerovium atom every week," explains Dr. Alexander Yakushev of GSI/FAIR, the spokesperson for the international experiment collaboration.

Six such decay chains were found in the data analysis. Since the setup is similar to that of the first GSI experiment, the newly obtained data could be combined with the two atoms observed at that time and analyzed together.

None of the decay chains appeared within the range of the silicon oxide-coated detector, indicating that flerovium does not form a substantial bond with silicon oxide. Instead, all were transported with the gas into the gold-coated portion of the apparatus within less than a tenth of a second.

The eight events formed two zones:a first in the region of the gold surface at room temperature, and a second in the later part of the chromatograph, at temperatures so low that a very thin layer of ice covered the gold, so that adsorption occurred on ice.

From experiments with lead, mercury and radon atoms, which served as representatives of heavy metals, weakly reactive metals as well as noble gases, it was known that lead forms a strong bond with silicon oxide, while mercury reaches the gold detector. Radon even flies over the first part of the gold detector at room temperature and is only partially retained at the lowest temperatures. Flerovium results could be compared with this behavior.

Apparently, two types of interaction of a flerovium species with the gold surface were observed. The deposition on gold at room temperature indicates the formation of a relatively strong chemical bond, which does not occur in noble gases. On the other hand, some of the atoms appear never to have had the opportunity to form such bonds and have been transported over long distances of the gold surface, down to the lowest temperatures.

This detector range represents a trap for all elemental species. This complicated behavior can be explained by the morphology of the gold surface:it consists of small gold clusters, at the boundaries of which very reactive sites occur, apparently allowing the flerovium to bond. The fact that some of the flerovium atoms were able to reach the cold region indicates that only the atoms that encountered such sites formed a bond, unlike mercury, which was retained on gold in any case.

Thus, the chemical reactivity of flerovium is weaker than that of the volatile metal mercury. The current data cannot completely rule out the possibility that the first deposition zone on gold at room temperature is due to the formation of flerovium molecules. It also follows from this hypothesis, though, that flerovium is chemically more reactive than a noble gas element.

The exotic plutonium target material for the production of the flerovium was provided in part by Lawrence Livermore National Laboratory (LLNL), U.S.. In the Department of Chemistry's TRIGA site at Johannes Gutenberg University Mainz (JGU), the material was electrolytically deposited onto thin titanium foils fabricated at GSI/FAIR.

"There is not much of this material available in the world, and we are fortunate to have been able to use it for these experiments that would not otherwise be possible," said Dr. Dawn Shaughnessy, head of the Nuclear and Chemical Sciences Division at LLNL. "This international collaboration brings together skills and expertise from around the world to solve difficult scientific problems and answer long-standing questions, such as the chemical properties of flerovium."

"Our accelerator experiment was complemented by a detailed study of the detector surface in collaboration with several GSI departments as well as the Department of Chemistry and the Institute of Physics at JGU. This has proven to be key to understanding the chemical character of flerovium. As a result, the data from the two earlier experiments are now understandable and compatible with our new conclusions," says Christoph Düllmann, professor of nuclear chemistry at JGU and head of the research groups at GSI and at the Helmholtz Institute Mainz (HIM), a collaboration between GSI and JGU.

How the relativistic effects affect its neighbors, the elements nihonium (element 113) and moscovium (element 115), which have also only been officially recognized in recent years, is the subject of subsequent experiments. Initial data have already been obtained as part of the FAIR Phase 0 program at GSI. Furthermore, the researchers expect that significantly more stable isotopes of flerovium exist, but these have not yet been found. However, the researchers now already know that they can expect to find a metallic element. + Utforska vidare

Nuclear physicist's voyage toward a mythical island