Lithium helium

Last updated
Lithium helium
Identifiers
3D model (JSmol)
PubChem CID
  • InChI=1S/He.Li
    Key: SINKHWKNPANGEK-UHFFFAOYSA-N
  • [He].[Li]
Properties
HeLi
Molar mass 10.94 g·mol−1
Related compounds
Other cations
Disodium helide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

LiHe is a compound of helium and lithium. The substance is a cold low-density gas made of Van der Waals molecules, each composed of a helium atom and lithium atom bound by van der Waals force. [1] The preparation of LiHe opens up the possibility to prepare other helium dimers, and beyond that multi-atom clusters that could be used to investigate Efimov states and Casimir retardation effects. [2]

Contents

Detection

It was detected in 2013. Previously 7Li4He was predicted to have a binding energy of 0.0039 cm−1 (7.7×10−8eV, 1.2×10−26J, or 6 mK [2] ), and a bond length of 28 Å. [1] Other van der Waals-bound helium molecules were previously known including Ag3He and He2. [1] Detection of LiHe was done via fluorescence. The lithium atom in the X2Σ state was excited to A2Π. The spectrum showed a pair of lines, each split into two with the hyperfine structure of 7Li. The lines had wavenumbers of 14902.563, 14902.591, 14902.740, and 14902.768 cm−1. The two pairs are separated by 0.177 cm−1. This is explained by two different vibrational states of the LiHe molecule: 1/2 and 3/2. [1] The bonding between the atoms is so low that it cannot withstand any rotation or greater vibration without breaking apart. The lowest rotation states would have energies of 40 and 80 mK, greater than the binding energy around 6 mK. [2]

LiHe was formed by laser ablation of lithium metal into a cryogenic helium buffer gas at a temperature between 1 and 5 K. The proportion of LiHe molecules was proportional to the density of He, and declined as the temperature increased. [1]

Properties

LiHe is polar and paramagnetic. [2]

The average separation between the lithium and helium atoms depends on the isotope. For 6LiHe the separation is 48.53 Å, but for 7LiHe the distance is much smaller at 28.15 Å on average. [3]

If the helium atom of LiHe is excited so that the 1s electron is promoted to 2s, it decays by transferring energy to ionise lithium, and the molecule breaks up. This is called interatomic Coulombic decay. The energy of the Li+ and He decay products is distributed in a curve that oscillates up and down about a dozen times. [3]

See also

Related Research Articles

Ionization or ionisation is the process by which an atom or a molecule acquires a negative or positive charge by gaining or losing electrons, often in conjunction with other chemical changes. The resulting electrically charged atom or molecule is called an ion. Ionization can result from the loss of an electron after collisions with subatomic particles, collisions with other atoms, molecules and ions, or through the interaction with electromagnetic radiation. Heterolytic bond cleavage and heterolytic substitution reactions can result in the formation of ion pairs. Ionization can occur through radioactive decay by the internal conversion process, in which an excited nucleus transfers its energy to one of the inner-shell electrons causing it to be ejected.

The Van der Waals radius, rw, of an atom is the radius of an imaginary hard sphere representing the distance of closest approach for another atom. It is named after Johannes Diderik van der Waals, winner of the 1910 Nobel Prize in Physics, as he was the first to recognise that atoms were not simply points and to demonstrate the physical consequences of their size through the Van der Waals equation of state.

Spectral line A distinctive narrow spectral feature

A spectral line is a dark or bright line in an otherwise uniform and continuous spectrum, resulting from emission or absorption of light in a narrow frequency range, compared with the nearby frequencies. Spectral lines are often used to identify atoms and molecules. These "fingerprints" can be compared to the previously collected ones of atoms and molecules, and are thus used to identify the atomic and molecular components of stars and planets, which would otherwise be impossible.

Dilithium, Li2, is a strongly electrophilic, diatomic molecule comprising two lithium atoms covalently bonded together. Li2 is known in the gas phase. It has a bond order of 1, an internuclear separation of 267.3 pm and a bond energy of 102 kJ/mol or 1.06eV in each bond. The electron configuration of Li2 may be written as σ2.

Although there are nine known isotopes of helium (2He), only helium-3 and helium-4 are stable. All radioisotopes are short-lived, the longest-lived being 6
He
with a half-life of 806.92±0.24 milliseconds. The least stable is 10
He
, with a half-life of 260±40 yoctoseconds, although it is possible that 2
He
may have an even shorter half-life.

Molecular solid Solid consisting of discrete molecules

A molecular solid is a solid consisting of discrete molecules. The cohesive forces that bind the molecules together are van der Waals forces, dipole-dipole interactions, quadrupole interactions, π-π interactions, hydrogen bonding, halogen bonding, London dispersion forces, and in some molecular solids, coulombic interactions. Van der Waals, dipole interactions, quadrupole interactions, π-π interactions, hydrogen bonding, and halogen bonding are typically much weaker than the forces holding together other solids: metallic, ionic, and network solids. Intermolecular interactions, typically do not involve delocalized electrons, unlike metallic and certain covalent bonds. Exceptions are charge-transfer complexes such as the tetrathiafulvane-tetracyanoquinodimethane (TTF-TCNQ), a radical ion salt. These differences in the strength of force and electronic characteristics from other types of solids give rise to the unique mechanical, electronic, and thermal properties of molecular solids.

Helium hydride ion Chemical compound

The helium hydride ion or hydridohelium(1+) ion or helonium is a cation (positively charged ion) with chemical formula HeH+. It consists of a helium atom bonded to a hydrogen atom, with one electron removed. It can also be viewed as protonated helium. It is the lightest heteronuclear ion, and is believed to be the first compound formed in the Universe after the Big Bang.

Van der Waals molecule Weakly bound complex of atoms or molecules

A Van der Waals molecule is a weakly bound complex of atoms or molecules held together by intermolecular attractions such as Van der Waals forces or by hydrogen bonds. The name originated in the beginning of the 1970s when stable molecular clusters were regularly observed in molecular beam microwave spectroscopy.

Positronium hydride

Positronium hydride, or hydrogen positride is an exotic molecule consisting of a hydrogen atom bound to an exotic atom of positronium. Its formula is PsH. It was predicted to exist in 1951 by A Ore, and subsequently studied theoretically, but was not observed until 1990. R. Pareja, R. Gonzalez from Madrid trapped positronium in hydrogen laden magnesia crystals. The trap was prepared by Yok Chen from the Oak Ridge National Laboratory. In this experiment the positrons were thermalized so that they were not traveling at high speed, and they then reacted with H ions in the crystal. In 1992 it was created in an experiment done by David M. Schrader and F.M. Jacobsen and others at the Aarhus University in Denmark. The researchers made the positronium hydride molecules by firing intense bursts of positrons into methane, which has the highest density of hydrogen atoms. Upon slowing down, the positrons were captured by ordinary electrons to form positronium atoms which then reacted with hydrogen atoms from the methane.

Surface phonon

In solid state physics, a surface phonon is the quantum of a lattice vibration mode associated with a solid surface. Similar to the ordinary lattice vibrations in a bulk solid, the nature of surface vibrations depends on details of periodicity and symmetry of a crystal structure. Surface vibrations are however distinct from the bulk vibrations, as they arise from the abrupt termination of a crystal structure at the surface of a solid. Knowledge of surface phonon dispersion gives important information related to the amount of surface relaxation, the existence and distance between an adsorbate and the surface, and information regarding presence, quantity, and type of defects existing on the surface.

Interatomic Coulombic decay (ICD) is a general, fundamental property of atoms and molecules which have neighbors. Interatomic (intermolecular) Coulombic decay is a very efficient interatomic (intermolecular) relaxation process of an electronically excited atom or molecule embedded in an environment. Without the environment the process cannot take place. Until now it has been mainly demonstrated for atomic and molecular clusters, independently of whether they are of van-der-Waals or hydrogen bonded type.

Xenon monochloride (XeCl) is an exciplex which is used in excimer lasers and excimer lamps emitting near ultraviolet light at 308 nm. It is most commonly used in medicine. Xenon monochloride was first synthesized in the 1960s. Its kinetic scheme is very complex and its state changes occur on a nanosecond timescale. In the gaseous state, at least two kinds of xenon monochloride are known: XeCl and Xe
2
Cl
, whereas complex aggregates form in the solid state in noble gas matrices. The excited state of xenon resembles halogens and it reacts with them to form excited molecular compounds.

The helium dimer is a van der Waals molecule with formula He2 consisting of two helium atoms. This chemical is the largest diatomic molecule—a molecule consisting of two atoms bonded together. The bond that holds this dimer together is so weak that it will break if the molecule rotates, or vibrates too much. It can only exist at very low cryogenic temperatures.

Helium is the smallest and the lightest noble gas and one of the most unreactive elements, so it was commonly considered that helium compounds cannot exist at all, or at least under normal conditions. Helium's first ionization energy of 24.57 eV is the highest of any element. Helium has a complete shell of electrons, and in this form the atom does not readily accept any extra electrons nor join with anything to make covalent compounds. The electron affinity is 0.080 eV, which is very close to zero. The helium atom is small with the radius of the outer electron shell at 0.29 Å. Helium is a very hard atom with a Pearson hardness hard and soft (Lewis) acids and bases of 12.3 eV. It has the lowest polarizability of any kind of atom, however, very weak van der Waals forces exist between helium and other atoms. This force may exceed repulsive forces, so at extremely low temperatures helium may form van der Waals molecules. Helium has the lowest boiling point of any known substance.

Helium trimer Chemical compound

The helium trimer is a weakly bound molecule consisting of three helium atoms. Van der Waals forces link the atoms together. The combination of three atoms is much more stable than the two-atom helium dimer. The three-atom combination of helium-4 atoms is an Efimov state. Helium-3 is predicted to form a trimer, although ground state dimers containing helium-3 are completely unstable.

Solid nitrogen

Solid nitrogen is the solid form of the element nitrogen. It is an important component of the surfaces of Pluto and outer moons of the Solar System such as Neptune's Triton. Under low or moderate pressure solid nitrogen contains dinitrogen molecules held together by London dispersion forces. At standard atmospheric pressure for Earth, this solid melts at 63.23 K, but this is not true at other pressures. Non-molecular forms of solid nitrogen produced by extreme pressures have a higher energy density than any other non-nuclear material.

Neon compounds are chemical compounds containing the element neon (Ne) with other molecules or elements from the periodic table. Compounds of the noble gas neon were believed not to exist, but there are now known to be molecular ions containing neon, as well as temporary excited neon-containing molecules called excimers. Several neutral neon molecules have also been predicted to be stable, but are yet to be discovered in nature. Neon has been shown to crystallize with other substances and form clathrates or Van der Waals solids.

Argon compounds, the chemical compounds that contain the element argon, are rarely encountered due to the inertness of the argon atom. However, compounds of argon have been detected in inert gas matrix isolation, cold gases, and plasmas, and molecular ions containing argon have been made and also detected in space. One solid interstitial compound of argon, Ar1C60 is stable at room temperature. Ar1C60 was discovered by the CSIRO.

The magnesium argide ion, MgAr+ is an ion composed of one ionised magnesium atom, Mg+ and an argon atom. It is important in inductively coupled plasma mass spectrometry and in the study of the field around the magnesium ion. The ionization potential of magnesium is lower than the first excitation state of argon, so the positive charge in MgAr+ will reside on the magnesium atom. Neutral MgAr molecules can also exist in an excited state.

Diargon Chemical compound

Diargon or the argon dimer is a molecule containing two argon atoms. Normally, this is only very weakly bound together by van der Waals forces. However, in an excited state, or ionised state, the two atoms can be more tightly bound together, with significant spectral features. At cryogenic temperatures, argon gas can have a few percent of diargon molecules.

References

  1. 1 2 3 4 5 Tariq, Naima; Taisan, Nada; Singh, Vijay; Weinstein, Jonathan (8 April 2013). "Spectroscopic Detection of the LiHe Molecule". Physical Review Letters. 110 (15): 153201. Bibcode:2013PhRvL.110o3201T. doi: 10.1103/PhysRevLett.110.153201 . PMID   25167262 . Retrieved 8 February 2015.
  2. 1 2 3 4 Friedrich, Bretislav (8 April 2013). "A Fragile Union Between Li and He Atoms". Physics. 6: 42. Bibcode:2013PhyOJ...6...42F. doi: 10.1103/Physics.6.42 .
  3. 1 2 Ben-Asher, Anael; Landau, Arie; Cederbaum, Lorenz S.; Moiseyev, Nimrod (24 July 2020). "Quantum Effects Dominating the Interatomic Coulombic Decay of an Extreme System". The Journal of Physical Chemistry Letters. 11 (16): 6600–6605. doi:10.1021/acs.jpclett.0c01974. PMID   32706968. S2CID   225444685.