Transactinide element

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In chemistry, transactinide elements (also, transactinides, or super-heavy elements) are the chemical elements with atomic numbers greater than those of the actinides, the heaviest of which is lawrencium (103).[1][2]

Transactinide elements are also transuranic elements, that is, have an atomic number greater than that of uranium (92), an actinide. The further distinction of having an atomic number greater than the actinides is significant in several ways:

  • The transactinide elements all have electrons in the 6d subshell in their ground state .
  • Except for rutherfordium and dubnium, even the longest-lasting isotopes of transactinide elements have extremely short half-lives, measured in seconds, or smaller units.
  • The element naming controversy involved the first five or six transactinide elements. These elements thus used systematic names for many years after their discovery had been confirmed. (Usually the systematic names are replaced with permanent names proposed by the discoverers relatively shortly after a discovery has been confirmed.)

Transactinides are radioactive and have only been obtained synthetically in laboratories. None of these elements has ever been collected in a macroscopic sample. Transactinide elements are all named after physicists and chemists or important locations involved in the synthesis of the elements.

Chemistry Nobelist Glenn T. Seaborg who first proposed the actinide concept which led to the acceptance of the actinide series also proposed the existence of a transactinide series ranging from element 104 to 121 and a superactinide series approximately spanning elements 122 to 153. The transactinide seaborgium is named in his honor.

IUPAC defines an element to exist if its lifetime is longer than 10−14 seconds, which is the time it takes for the nucleus to form an electronic cloud.[3]

List of the known transactinide elements[edit]

Super heavy elements (polyatomic).svg

* The synthesis of these elements has not been officially attested by IUPAC, while in several cases previous syntheses have been confirmed by other institutions or other methods. The names and symbols given are provisional as no names for the elements have been agreed on.

Characteristics[edit]

Due to their short half-lives and the low yield of the nuclear reactions that produce them, new methods have had to be created to determine their gas-phase and solution chemistry based on very small samples of a few atoms each. Relativistic effects become very important in this region of the periodic table, causing the filled 7s orbitals, empty 7p orbitals, and filling 6d orbitals to all contract inwards toward the atomic nucleus. This causes a relativistic stabilization of the 7s electrons and makes the 7p orbitals accessible in low excitation states.[2]

Elements 104 to 112, rutherfordium through copernicium, form the 6d series of transition elements: for elements 104–108 and 112, experimental evidence shows them to behave as expected for their position in the periodic table. They are expected to have ionic radii between those of their 5d transition metal homologs and their actinide pseudohomologs: for example, Rf4+ is calculated to have ionic radius 76 pm, between the values for Hf4+ (71 pm) and Th4+ (94 pm). Their ions should also be less polarizable than those of their 5d homologs. Relativistic effects are expected to reach a maximum at the end of this series, at roentgenium (element 111) and copernicium (element 112). Nevertheless, many important properties of the transactinides are still not yet known experimentally, though theoretical calculations have been performed.[2]

Elements 113 to 118 should form a 7p series, completing the seventh period in the periodic table. Their chemistry will be greatly influenced by the very strong relativistic stabilization of the 7s electrons and a strong spin-orbit coupling effect "tearing" the 7p subshell apart into two sections, one more stabilized (7p1/2, holding two electrons) and one more destabilized (7p3/2, holding four electrons). Additionally, the 6d electrons are still destabilized in this region and hence may be able to contribute some transition metal character to the first few 7p elements. Lower oxidation states should be stabilized here, continuing group trends, as both the 7s and 7p1/2 electrons exhibit the inert pair effect. These elements are expected to largely continue to follow group trends, though with relativistic effects playing an increasingly larger role: this prediction has only been verified for element 114, flerovium, which has been determined to behave like a typical metal in the carbon group, albeit being quite unreactive due to its predicted stable quasi-closed shell configuration of [Rn]5f146d107s27p2.[2]

Element 118 is the last element that has been claimed to have been synthesized. The next two elements, elements 119 and 120, should form an 8s series and be an alkali and alkaline earth metal respectively. The 8s electrons are expected to be relativistically stabilized, so that the trend towards higher reactivity down these groups will reverse direction and the elements will behave more like their period 5 homologs, rubidium and strontium. Nevertheless, the 7p3/2 orbital is still relativistically destabilized, potentially giving these elements larger ionic radii and perhaps even being able to participate chemically. In this region, the 8p electrons are also relativistically stabilized, resulting in a ground-state 8s28p1 valence electron configuration for element 121. Large changes are expected to occur in the subshell structure in going from element 120 to element 121: for example, the radius of the 5g orbitals should drop drastically, from 25 Bohr units in element 120 in the excited [Uuo]5g18s1 configuration to 0.8 Bohr units in element 121 in the excited [Uuo]5g17d18s1 configuration, in a phenomenon called "radial collapse" that occurs at element 125. Element 122 should add a further 7d electron to element 121's electron configuration. Elements 121 and 122 should be homologs of actinium and thorium, respectively.[2]

Beyond element 121, the superactinide series is expected to begin, when the 8s electrons and the filling 8p1/2, 7d3/2, 6f5/2, and 5g7/2 subshells determine the chemistry of these elements. Complete and accurate CCSD calculations are not available for elements beyond 122 because of the extreme complexity of the situation: the 5g, 6f, and 7d orbitals should have about the same energy level, and in the region of element 160 the 9s, 8p3/2, and 9p1/2 orbitals should also be about equal in energy. This will cause the electron shells to mix so that the block concept no longer applies very well, and will also result in novel chemical properties that will make positioning these elements in a periodic table very difficult. For example, element 164 is expected to mix characteristics of the elements of group 10, 12, and 18.[2]

See also[edit]

References[edit]

  1. ^ IUPAC Provisional Recommendations for the Nomenclature of Inorganic Chemistry (2004)[dead link] (online draft of an updated version of the "Red Book" IR 3-6)
  2. ^ a b c d e f Morss, Lester R.; Edelstein, Norman M.; Fuger, Jean, eds. (2006). The Chemistry of the Actinide and Transactinide Elements (3rd ed.). Dordrecht, The Netherlands: Springer. ISBN 978-1-4020-3555-5. 
  3. ^ Kernchemie