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===Physical and atomic===
===Physical and atomic===
In the [[periodic table]], livermorium is a member of group 16, the chalcogens, in the [[periodic table]], below [[oxygen]], [[sulfur]], [[selenium]], [[tellurium]], and polonium. Every previous chalcogen has six electrons in its valence shell, forming a [[valence electron]] configuration of ns<sup>2</sup>np<sup>4</sup>. In livermorium's case, the trend should be continued and the valence electron configuration is predicted to be 7s<sup>2</sup>7p<sup>4</sup>;<ref name="Haire"/> therefore, livermorium will behave similarly to its lighter [[congener (chemistry)|congeners]] in many respects. However, notable differences are likely to arise; a largely contributing effect is the [[spin–orbit interaction|spin–orbit (SO) interaction]]—the mutual interaction between the electrons' motion and [[spin (physics)|spin]]. It is especially strong for the superheavy elements, because their electrons move much faster than in lighter atoms, at velocities comparable to the [[speed of light]].<ref name=Thayer/> In relation to livermorium atoms, it lowers the 7s and the 7p electron energy levels<!--|level is an important word. Lv has no 8s electrons but they've been shown to affect its chem---> (stabilizing the corresponding electrons), but two of the 7p electron energy levels are stabilized more than the other four.<ref name="Faegri">{{Cite journal|last1=Faegri |first1=K.|last2=Saue |first2=T.|year=2001|title=Diatomic molecules between very heavy elements of group 13 and group 17: A study of relativistic effects on bonding|journal=[[Journal of Chemical Physics]]|volume=115 |issue=6 |pages=2456|bibcode=2001JChPh.115.2456F|doi=10.1063/1.1385366 }}</ref> The stabilization of the 7s electrons is called the [[inert pair effect]], and the effect "tearing" the 7p subshell into the more stabilized and the less stabilized parts is called subshell splitting. Computation chemists see the split as a change of the second ([[azimuthal quantum number|azimuthal]]) [[quantum number]] ''l'' from 1 to {{frac|1|2}} and {{frac|3|2}} for the more stabilized and less stabilized parts of the 7p subshell, respectively.<ref name=Thayer/>{{efn|The quantum number corresponds to the letter in the electron orbital name: 0 to s, 1 to p, 2 to d, etc. See [[azimuthal quantum number]] for more information.}} For many theoretical purposes, the valence electron configuration may be represented to reflect the 7p subshell split as 7s{{su|p=2|w=70%}}7p{{su|b=1/2|p=2|w=70%}}7p{{su|b=3/2|p=2|w=70%}}.<ref name=Haire/> These effects cause livermorium's chemistry to be somewhat different from that of its lighter [[congener (chemistry)|congeners]].
{{empty section|date=September 2014}}

The valence electrons of livermorium fall into three subshells: 7s, 7p<sub>1/2</sub>, and 7p<sub>3/2</sub>, each having two electrons. The first two of these are relativistically stabilized and hence behave as [[inert pair effect|inert pairs]], while the last is relativistically destabilized and can easily participate in chemistry.<ref name=Haire/> The inert pair effects in livermorium should be even stronger than for polonium and hence the +2 [[oxidation state]] becomes more stable than the +4 state, which would be stabilized only by the most [[electronegative]] [[ligand (chemistry)|ligands]]; this is reflected in the expected [[ionization energy|ionization energies]] of livermorium, where there are large gaps between the second and third ionization energies (corresponding to the breaching of the unreactive 7p<sub>1/2</sub> shell) and fourth and fifth ionization energies.<ref name=BFricke/> Indeed the 7s electrons are expected to be so inert that the +6 state will not be possible to attain.<ref name=Haire/> The [[melting point|melting]] and [[boiling point]]s of livermorium are expected to continue the trends down the chalcogens; thus livermorium should melt at a higher temperature than polonium, but boil at a lower temperature.<ref name="B&K"/> It should also be [[density|denser]] than polonium (Lv: 12.9&nbsp;g/cm<sup>3</sup>; α-Po: 9.2&nbsp;g/cm<sup>3</sup>).<ref name=BFricke/> The electron of the [[hydrogen-like atom|hydrogen-like]] livermorium atom (oxidized so that it only has one electron, Lv<sup>115+</sup>) is expected to move so fast that it has a mass 1.86 times that of a stationary electron, due to [[relativistic quantum chemistry|relativistic effects]]. For comparison, the figures for hydrogen-like polonium and tellurium are expected to be 1.26 and 1.080 respectively.<ref name=Thayer>{{cite book|title=Chemistry of Heavier Main Group Elements|last=Thayer|first=John S.|doi=10.1007/9781402099755_2|year=2010|pages=63–67, 83}}</ref>


===Chemical===
===Chemical===

Revision as of 11:51, 15 September 2014

Livermorium, 116Lv
Livermorium
Pronunciation/ˌlɪvərˈmɔːriəm/ ⓘ ​(LIV-ər-MOR-ee-əm)
Mass number[293] (data not decisive)[a]
Livermorium in the periodic table
Hydrogen Helium
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon
Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
Caesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury (element) Thallium Lead Bismuth Polonium Astatine Radon
Francium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson
Po
↑
Lv
↓
—
moscovium ← livermorium → tennessine
Atomic number (Z)116
Groupgroup 16 (chalcogens)
Periodperiod 7
Block  p-block
Electron configuration[Rn] 5f14 6d10 7s2 7p4 (predicted)[2]
Electrons per shell2, 8, 18, 32, 32, 18, 6 (predicted)
Physical properties
Phase at STPsolid (predicted)[2][3]
Melting point637–780 K ​(364–507 °C, ​687–944 °F) (extrapolated)[3]
Boiling point1035–1135 K ​(762–862 °C, ​1403–1583 °F) (extrapolated)[3]
Density (near r.t.)12.9 g/cm3 (predicted)[2]
Heat of fusion7.61 kJ/mol (extrapolated)[3]
Heat of vaporization42 kJ/mol (predicted)[4]
Atomic properties
Oxidation statescommon: (none)
(−2),[5] (+4)
Ionization energies
  • 1st: 663.9 kJ/mol (predicted)[6]
  • 2nd: 1330 kJ/mol (predicted)[4]
  • 3rd: 2850 kJ/mol (predicted)[4]
  • (more)
Atomic radiusempirical: 183 pm (predicted)[4]
Covalent radius162–166 pm (extrapolated)[3]
Other properties
Natural occurrencesynthetic
CAS Number54100-71-9
History
Namingafter Lawrence Livermore National Laboratory,[7] itself named partly after Livermore, California
DiscoveryJoint Institute for Nuclear Research and Lawrence Livermore National Laboratory (2000)
Isotopes of livermorium
Main isotopes[1] Decay
abun­dance half-life (t1/2) mode pro­duct
290Lv synth 8.3 ms α 286Fl
SF –
291Lv synth 19 ms α 287Fl
292Lv synth 16 ms α 288Fl
293Lv synth 57 ms α 289Fl
293mLv synth 20 ms α ?
 Category: Livermorium
| references

Livermorium is the synthetic superheavy element with the symbol Lv and atomic number 116. It is an extremely radioactive element that has only been created in the laboratory and has not been observed in nature. The element is named after the Lawrence Livermore National Laboratory in the United States, which collaborated with the Joint Institute for Nuclear Research in Dubna, Russia to discover livermorium in 2000. The name of the laboratory in turn honors the city of Livermore, California where it is located, which in turn was named after the rancher and landowner Robert Livermore. The name was adopted by IUPAC on May 30, 2012.[7] About 35 atoms of livermorium have been produced, either directly or as a decay product of ununoctium, and they all had mass numbers from 290 to 293. Its most stable isotope is livermorium-293 with a half-life of about 60 milliseconds.

In the periodic table, it is a p-block transactinide element. It is a member of the 7th period and is placed in group 16 as the heaviest chalcogen, although it has not been confirmed to behave as the heavier homologue to the chalcogen polonium. Livermorium is calculated to have some similar properties to its lighter homologues, oxygen, sulfur, selenium, tellurium, and polonium, although it should also show several major differences from them.

History

Unsuccessful synthesis attempts

In late 1998, Polish physicist Robert Smolańczuk published calculations on the fusion of atomic nuclei towards the synthesis of superheavy atoms, including ununoctium.[8] His calculations suggested that it might be possible to make ununoctium and livermorium by fusing lead with krypton under carefully controlled conditions.[8]

In 1999, researchers at Lawrence Berkeley National Laboratory made use of these predictions and announced the discovery of livermorium and ununoctium, in a paper published in Physical Review Letters,[9] and very soon after the results were reported in Science.[10] The researchers reported to have performed the reaction

86
36Kr + 208
82Pb → The element Ununoctium does not exist. + n.

The following year, they published a retraction after researchers at other laboratories were unable to duplicate the results and the Berkeley lab itself was unable to duplicate them as well.[11] In June 2002, the director of the lab announced that the original claim of the discovery of these two elements had been based on data fabricated by principal author Victor Ninov.[12][13]

Discovery

Livermorium was first synthesized on July 19, 2000, when scientists at Dubna (JINR) bombarded a curium-248 target with accelerated calcium-48 ions. A single atom was detected, decaying by alpha emission with decay energy 10.54 MeV to an isotope of flerovium. The results were published in December 2000.[14]

248
96Cm + 48
20Ca → 296
116Lv* → 293
116Lv + 3 1
0n

The daughter flerovium isotope had properties matching those of a flerovium isotope first synthesized in June 1999, which was originally assigned to 288Fl,[14] implying an assignment of the parent livermorium isotope to 292Lv. Later work in December 2002 indicated that the synthesized flerovium isotope was actually 289Lv, and hence the assignment of the synthesized livermorium atom was correspondingly altered to 293Lv.[15]

Road to confirmation

Two further atoms were reported by the institute during their second experiment between April–May 2001.[16] In the same experiment they also detected a decay chain which corresponded to the first observed decay of flerovium in December 1998, which had been assigned to 289Fl.[16] This flerovium isotope has not been observed again in a repeat of the same reaction, and later it was found that 289Fl did not have these decay properties and that the first observed flerovium atom may have been the nuclear isomer 289mFl.[14][17] However, its detection in this series of experiments indicates the possibility of the decay of an isomer of livermorium, namely 293mLv, or a rare decay branch of the already-discovered state, 293Lv, in which the first alpha particle was not detected. Further research is required to positively assign this activity.[14][17]

The team repeated the experiment in April–May 2005 and detected 8 atoms of livermorium. The measured decay data confirmed the assignment of the first-discovered isotope as 293Lv. In this run, the team also observed the isotope 292Lv for the first time.[15] In further experiments from 2004 to 2006, the team replaced the curium-248 target with the lighter curium isotope curium-245. Here evidence was found for the two isotopes 290Lv and 291Lv.[18]

In May 2009, the IUPAC/IUPAP Joint Working Party reported on the discovery of copernicium and acknowledged the discovery of the isotope 283Cn.[19] This implied the de facto discovery of the livermorium-291 isotope, from the acknowledgment of the data relating to its granddaughter 283Cn. Also in 2009, confirmation from Berkeley and the Gesellschaft für Schwerionenforschung (GSI) in Germany came for the flerovium isotopes 286 to 289, immediate daughters of the four known livermorium isotopes. In 2011, IUPAC evaluated the Dubna team experiments of 2000–2006. Whereas they found the early data inconclusive, the results of 2004–2006 were accepted as identification of livermorium, and the element was officially recognized as having been discovered.[18]

Naming

Using Mendeleev's nomenclature for unnamed and undiscovered elements, livermorium is sometimes called eka-polonium.[20] In 1979 IUPAC recommended that the placeholder systematic element name ununhexium (with the corresponding symbol of Uuh)[21] be used until the discovery of the element is confirmed and a name is decided on. These recommendations were largely ignored among scientists, who called it "element 116", with the symbol of (116) or even simply 116.[2]

According to IUPAC recommendations, the discoverer or discoverers of a new element have the right to suggest a name.[22] The discovery of livermorium was recognized by the Joint Working Group (JWG) of IUPAC on 1 June 2011, along with that of flerovium.[18] According to the vice-director of JINR, the Dubna team originally wanted to name element 116 moscovium, after the Moscow Oblast in which Dubna is located.[23] However, the name livermorium and the symbol Lv were adopted on May 31, 2012[7] after an approval process by the IUPAC.[24] The name recognises the Lawrence Livermore National Laboratory, within the city of Livermore, California, USA, which collaborated with JINR on the discovery. The city in turn is named after the American rancher Robert Livermore, a naturalized Mexican citizen of English birth.[7]

Predicted properties

Nuclear stability and isotopes

Main article: Isotopes of livermorium
The expected location of the island of stability

Livermorium is expected to be in the middle of an island of stability centered around copernicium (element 112) and flerovium (element 114): the reasons for the presence of this island are however still not well understood.[25][26] Due to the expected high fission barriers, any nucleus within this island of stability exclusively decays by alpha decay and perhaps some electron capture and beta decay.[27] While the known isotopes of livermorium do not actually have enough neutrons to be on the island of stability, they can be seen to approach the island as in general, the heavier isotopes are the longer-lived ones.[14][18]

Important information could be gained regarding the properties of superheavy nuclei by the synthesis of more livermorium isotopes, specifically those with a few neutrons more or less than the known ones – 286Lv, 287Lv, 288Lv, 289Lv, 294Lv, and 295Lv. This is possible because there are many reasonably long-lived isotopes of curium that can be used to make a target.[25] The light isotopes can be made by fusing curium-243 with calcium-48. They would undergo a chain of alpha decays, ending at transactinide isotopes that are too light to achieve by hot fusion and too heavy to be produced by cold fusion.[25] In hot fusion reactions, very light, high-energy projectiles are accelerated toward very heavy targets (actinides), giving rise to compound nuclei at high excitation energy (~40–50 MeV) that may either fission or evaporate several (3 to 5) neutrons.[28] In cold fusion reactions, the produced fused nuclei have a relatively low excitation energy (~10–20 MeV), which decreases the probability that these products will undergo fission reactions. As the fused nuclei cool to the ground state, they require emission of only one or two neutrons. However, hot fusion reactions tend to produce more neutron-rich products because the actinides have the highest neutron-to-proton ratios of any elements that can presently be made in macroscopic quantities.[29] The latter is a distinct concept from that of where nuclear fusion claimed to be achieved at room temperature conditions (see cold fusion).[30]

The synthesis of 294Lv and 295Lv can be accomplished by fusing the heavy curium isotope curium-250 with calcium-48. The cross section of this nuclear reaction would be about 1 picobarn.[25] After a few alpha decays, these livermorium isotopes would reach nuclides at the line of beta stability. Additionally, electron capture may also become an important decay mode in this region, allowing affected nuclei to reach the middle of the island. For example, 295Lv would alpha decay to 291Fl, which would undergo successive electron capture to 291Uut and then 291Cn which is expected to be in the middle of the island of stability and have a half-life of about 1200 years, affording the most likely hope of reaching the middle of the island using current technology. A drawback is that the decay properties of superheavy nuclei this close to the line of beta stability are largely unexplored.[25]

Other possibilities to synthesize nuclei on the island of stability include quasifission (partial fusion followed by fission) of a massive nucleus.[31] Such nuclei tend to fission, expelling doubly-magic or nearly doubly-magic fragments such as calcium-40, tin-132, lead-208, or bismuth-209.[32] Recently it has been shown that the multi-nucleon transfer reactions in collisions of actinide nuclei (such as uranium and curium) might be used to synthesize the neutron-rich superheavy nuclei located at the island of stability,[31] although formation of the lighter elements nobelium or seaborgium is more favored.[25] One last possibility to synthesize isotopes near the island is to use controlled nuclear explosions to create a neutron flux high enough to bypass the gaps of instability at 258–260Fm and at mass number 275 (atomic numbers 104 to 108), mimicking the r-process in which the actinides were first produced in nature and the gap of instability around radon bypassed.[25] Some such isotopes (especially 291Cn and 293Cn) may even have been synthesized in nature, but would have decayed away far too quickly (with half-lives of only thousands of years) and be produced in far too small quantities (about 10−12 the abundance of lead) to be detectable as primordial nuclides today outside cosmic rays.[25]

Physical and atomic

In the periodic table, livermorium is a member of group 16, the chalcogens, in the periodic table, below oxygen, sulfur, selenium, tellurium, and polonium. Every previous chalcogen has six electrons in its valence shell, forming a valence electron configuration of ns2np4. In livermorium's case, the trend should be continued and the valence electron configuration is predicted to be 7s27p4;[2] therefore, livermorium will behave similarly to its lighter congeners in many respects. However, notable differences are likely to arise; a largely contributing effect is the spin–orbit (SO) interaction—the mutual interaction between the electrons' motion and spin. It is especially strong for the superheavy elements, because their electrons move much faster than in lighter atoms, at velocities comparable to the speed of light.[33] In relation to livermorium atoms, it lowers the 7s and the 7p electron energy levels (stabilizing the corresponding electrons), but two of the 7p electron energy levels are stabilized more than the other four.[34] The stabilization of the 7s electrons is called the inert pair effect, and the effect "tearing" the 7p subshell into the more stabilized and the less stabilized parts is called subshell splitting. Computation chemists see the split as a change of the second (azimuthal) quantum number l from 1 to 1⁄2 and 3⁄2 for the more stabilized and less stabilized parts of the 7p subshell, respectively.[33][b] For many theoretical purposes, the valence electron configuration may be represented to reflect the 7p subshell split as 7s2
7p2
1/27p2
3/2.[2] These effects cause livermorium's chemistry to be somewhat different from that of its lighter congeners.

The valence electrons of livermorium fall into three subshells: 7s, 7p1/2, and 7p3/2, each having two electrons. The first two of these are relativistically stabilized and hence behave as inert pairs, while the last is relativistically destabilized and can easily participate in chemistry.[2] The inert pair effects in livermorium should be even stronger than for polonium and hence the +2 oxidation state becomes more stable than the +4 state, which would be stabilized only by the most electronegative ligands; this is reflected in the expected ionization energies of livermorium, where there are large gaps between the second and third ionization energies (corresponding to the breaching of the unreactive 7p1/2 shell) and fourth and fifth ionization energies.[27] Indeed the 7s electrons are expected to be so inert that the +6 state will not be possible to attain.[2] The melting and boiling points of livermorium are expected to continue the trends down the chalcogens; thus livermorium should melt at a higher temperature than polonium, but boil at a lower temperature.[3] It should also be denser than polonium (Lv: 12.9 g/cm3; α-Po: 9.2 g/cm3).[27] The electron of the hydrogen-like livermorium atom (oxidized so that it only has one electron, Lv115+) is expected to move so fast that it has a mass 1.86 times that of a stationary electron, due to relativistic effects. For comparison, the figures for hydrogen-like polonium and tellurium are expected to be 1.26 and 1.080 respectively.[33]

Chemical

Livermorium is projected to be the fourth member of the 7p series of chemical elements and the heaviest chalcogen in the Periodic Table, below polonium. The group oxidation state of +6 is known for all the members apart from oxygen which lacks available d-orbitals for expansion and is limited to a maximum +2 state, exhibited in the fluoride OF2. The +4 is known for sulfur, selenium, tellurium, and polonium, undergoing a shift in stability from reducing for S(IV) and Se(IV) to oxidizing in Po(IV). Tellurium(IV) is the most stable for this element. This suggests a decreasing stability for the higher oxidation states as the group is descended and livermorium should portray an oxidizing +4 state and a more stable +2 state. The lighter members are also known to form a −2 state as oxide, sulfide, selenide, telluride, and polonide.

The possible chemistry of livermorium can be extrapolated from that of polonium. It should therefore undergo oxidation to a dioxide, LvO2, although a trioxide, LvO3 is plausible, but unlikely. The stability of a +2 state should manifest itself in the formation of a simple monoxide, LvO. Fluorination will likely result in a tetrafluoride, LvF4 and/or a difluoride, LvF2; a hexafluoride, LvF6, is possible but unlikely. Chlorination and bromination may well stop at the corresponding dihalides, LvCl2 and LvBr2. Oxidation by iodine should certainly stop at LvI2 and may even be inert to this element.[citation needed] The heavier livermorium dihalides are predicted to be linear, but the lighter ones are predicted to be bent.[35]

Experimental chemistry

Unambiguous determination of the chemical characteristics of livermorium has yet to have been established.[36][37] In 2011, experiments were conducted to create ununtrium, flerovium, and ununpentium isotopes in the reactions between calcium-48 projectiles and targets of americium-243 and plutonium-244. However, the targets included lead and bismuth impurities and hence some isotopes of bismuth and polonium were generated in nucleon transfer reactions. This, while an unforeseen complication, could give information that would help in the future chemical investigation of the heavier homologs of bismuth and polonium, which are respectively ununpentium and livermorium.[37] The produced nuclides bismuth-213 and polonium-212m were transported as the hydrides 213BiH3 and 212mPoH2 at 850 °C through a quartz wool filter unit held with tantalum, showing that these hydrides were surprisingly thermally stable, although their heavier congeners UupH3 and LvH2 would be expected to be less thermally stable from simple extrapolation of periodic trends in the p-block.[37] Further calculations on the stability and electronic structure of BiH3, UupH3, PoH2, and LvH2 are needed before chemical investigations take place. However, ununpentium and livermorium are expected to be volatile enough as pure elements for them to be chemically investigated in the near future. The chief barrier to their chemical investigation at present is the lack of known isotopes of these elements which are long-lived enough.[37]

See also

References

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