Argonium

Last updated
Argonium
Argonium-3D-vdW.png
Names
IUPAC name
Argonium ion
Other names
Hydridoargon(1+)
argon hydride cation [1]
protonated argon [2]
Identifiers
3D model (JSmol)
  • InChI=1S/ArH/h1H/q+1 Yes check.svgY[ NIST ]
    Key: TVQSUVFYDVJWLI-UHFFFAOYSA-N Yes check.svgY[ NIST ]
  • [ArH+]
Properties
ArH+
Molar mass 40.956 g·mol−1
Conjugate base Argon
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Argonium (also called the argon hydride cation, the hydridoargon(1+) ion, or protonated argon; chemical formula ArH+) is a cation combining a proton and an argon atom. It can be made in an electric discharge, and was the first noble gas molecular ion to be found in interstellar space. [3]

Contents

Properties

Argonium is isoelectronic with hydrogen chloride. Its dipole moment is 2.18  D for the ground state. [4] The binding energy is 369 kJ mol−1 [5] (3.9 eV [6] ). This is smaller than that of H+
3
and many other protonated species, but more than that of H+
2
. [5]

Rotationless radiative lifetimes of different vibrational states vary with isotope and become shorter for the more rapid high-energy vibrations:

Lifetimes (ms) [7]
vArH+ArD+
12.289.09
21.204.71
30.853.27
40.642.55
50.462.11

The force constant in the bond is calculated at 3.88 mdyne/Å2. [8]

Reactions

But the reverse reaction happens:

Ar+ + H2 has a cross section of 10−18 m2 for low energy. It has a steep drop off for energies over 100 eV [9] Ar + H+
2
has a cross sectional area of 6×10−19 m2 for low energy H+
2
, but when the energy exceeds 10 eV yield reduces, and more Ar+ and H2 is produced instead. [9]

Ar + H+
3
has a maximum yield of ArH+ for energies between 0.75 and 1 eV with a cross section of 5×10−20 m2. 0.6 eV is needed to make the reaction proceed forward. Over 4 eV more Ar+ and H starts to appear. [9]

Argonium is also produced from Ar+ ions produced by cosmic rays and X-rays from neutral argon.

When ArH+ encounters an electron, dissociative recombination can occur, but it is extremely slow for lower energy electrons, allowing ArH+ to survive for a much longer time than many other similar protonated cations.

Because ionisation potential of argon atoms is lower than that of the hydrogen molecule (in contrast to that of helium or neon), the argon ion reacts with molecular hydrogen, but for helium and neon ions, they will strip an electron from a hydrogen molecule. [5]

Spectrum

Artificial ArH+ made from earthly argon contains mostly the isotope 40Ar rather than the cosmically abundant 36Ar. Artificially it is made by an electric discharge through an argon–hydrogen mixture. [10] Brault and Davis were the first to detect the molecule using infrared spectroscopy to observe vibration–rotation bands. [10]

Far infrared spectrum of 40Ar1H+ [10] 36Ar38Ar [4]
Transitionobserved frequency
JGHz
1←0615.8584617.525615.85815
2←11231.27121234.602
3←21845.7937
4←32458.9819
5←43080.3921
6←53679.5835
7←64286.1150
21←2012258.483
22←2112774.366
23←2213281.119

The UV spectrum has two absorption points resulting in the ion breaking up. The 11.2 eV conversion to the B1Π state has a low dipole and so does not absorb much. A 15.8 eV to a repulsive A1Σ+ state is at a shorter wavelength than the Lyman limit, and so there are very few photons around to do this in space. [5]

Natural occurrence

ArH+ occurs in interstellar diffuse atomic hydrogen gas. For argonium to form, the fraction of molecular hydrogen H2 must be in the range 0.0001 to 0.001. Different molecular ions form in correlation with different concentrations of H2. Argonium is detected by its absorption lines at 617.525 GHz (J = 1→0), and 1234.602 GHz (J = 2→1). These lines are due to the isotopolog 36Ar1H+ undergoing rotational transitions. The lines have been detected in the direction of the galactic centre SgrB2(M) and SgrB2(N), G34.26+0.15, W31C (G10.62−0.39), W49(N), and W51e, however where absorption lines are observed, argonium is not likely to be in the microwave source, but instead in the gas in front of it. [5] Emission lines are found in the Crab Nebula. [6]

In the Crab Nebula ArH+ occurs in several spots revealed by emission lines. The strongest place is in the Southern Filament. This is also the place with the strongest concentration of Ar+ and Ar2+ ions. [6] The column density of ArH+ in the Crab Nebula is between 1012 and 1013 atoms per square centimeter. [6] Possible the energy required to excite the ions so that then can emit comes from collisions with electrons or hydrogen molecules. [6] Towards the Milky Way centre the column density of ArH+ is around 2×1013 cm−2. [5]

Two isotopologs of argonium 36ArH+ and 38ArH+ are known to be in a distant unnamed galaxy with a redshift of z = 0.88582 (7.5 billion light years away) which is on the line of sight to the blazar PKS 1830−211. [4]

Electron neutralization and destruction of argonium outcompletes the formation rate in space if the H2 concentration is below 1 in 10−4. [11]

History

Using the McMath solar Fourier transform spectrometer at Kitt Peak National Observatory, James W. Brault and Sumner P. Davis observed ArH+ vibration-rotation infrared lines for the first time. [12] J. W. C. Johns also observed the infrared spectrum. [13]

Use

Argon facilitates the reaction of tritium (T2) with double bonds in fatty acids by forming an ArT+ (tritium argonium) intermediate. [14] When gold is sputtered with an argon-hydrogen plasma, the actual displacement of gold is done by ArH+. [15]

Related Research Articles

<span class="mw-page-title-main">Argon</span> Chemical element, symbol Ar and atomic number 18

Argon is a chemical element; it has symbol Ar and atomic number 18. It is in group 18 of the periodic table and is a noble gas. Argon is the third most abundant gas in Earth's atmosphere, at 0.934%. It is more than twice as abundant as water vapor, 23 times as abundant as carbon dioxide, and more than 500 times as abundant as neon. Argon is the most abundant noble gas in Earth's crust, comprising 0.00015% of the crust.

<span class="mw-page-title-main">Diatomic molecule</span> Molecule composed of any two atoms

Diatomic molecules are molecules composed of only two atoms, of the same or different chemical elements. If a diatomic molecule consists of two atoms of the same element, such as hydrogen or oxygen, then it is said to be homonuclear. Otherwise, if a diatomic molecule consists of two different atoms, such as carbon monoxide or nitric oxide, the molecule is said to be heteronuclear. The bond in a homonuclear diatomic molecule is non-polar.

<span class="mw-page-title-main">Hydrogen</span> Chemical element, symbol H and atomic number 1

Hydrogen is a chemical element; it has symbol H and atomic number 1. It is the lightest element and, at standard conditions, is a gas of diatomic molecules with the formula H2, sometimes called dihydrogen, but more commonly called hydrogen gas, molecular hydrogen or simply hydrogen. It is colorless, odorless, tasteless, non-toxic, and highly combustible. Constituting approximately 75% of all normal matter, hydrogen is the most abundant chemical substance in the universe. Stars, including the Sun, primarily consist of hydrogen in a plasma state, while on Earth, hydrogen is found in water, organic compounds, and other molecular forms. The most common isotope of hydrogen consists of one proton, one electron, and no neutrons.

<span class="mw-page-title-main">Molecular cloud</span> Type of interstellar cloud

A molecular cloud, sometimes called a stellar nursery (if star formation is occurring within), is a type of interstellar cloud, the density and size of which permit absorption nebulae, the formation of molecules (most commonly molecular hydrogen, H2), and the formation of H II regions. This is in contrast to other areas of the interstellar medium that contain predominantly ionized gas.

<span class="mw-page-title-main">Interstellar medium</span> Matter and radiation in the space between the star systems in a galaxy

In astronomy, the interstellar medium (ISM) is the matter and radiation that exists in the space between the star systems in a galaxy. This matter includes gas in ionic, atomic, and molecular form, as well as dust and cosmic rays. It fills interstellar space and blends smoothly into the surrounding intergalactic space. The energy that occupies the same volume, in the form of electromagnetic radiation, is the interstellar radiation field. Although the density of atoms in the ISM is usually far below that in the best laboratory vacuums, the mean free path between collisions is short compared to typical interstellar lengths, so on these scales the ISM behaves as a gas (more precisely, as a plasma: it is everywhere at least slightly ionized), responding to pressure forces, and not as a collection of non-interacting particles.

In chemistry, noble gas compounds are chemical compounds that include an element from the noble gases, group 18 of the periodic table. Although the noble gases are generally unreactive elements, many such compounds have been observed, particularly involving the element xenon.

Argon (18Ar) has 26 known isotopes, from 29Ar to 54Ar and 1 isomer (32mAr), of which three are stable. On the Earth, 40Ar makes up 99.6% of natural argon. The longest-lived radioactive isotopes are 39Ar with a half-life of 268 years, 42Ar with a half-life of 32.9 years, and 37Ar with a half-life of 35.04 days. All other isotopes have half-lives of less than two hours, and most less than one minute. The least stable is 29Ar with a half-life of approximately 4×10−20 seconds.

<span class="mw-page-title-main">Trihydrogen cation</span> Polyatomic ion (H₃, charge +1)

The trihydrogen cation or protonated molecular hydrogen is a cation with formula H+
3
, consisting of three hydrogen nuclei (protons) sharing two electrons.

<span class="mw-page-title-main">Ethynyl radical</span> Hydrocarbon compound (•CCH)

The ethynyl radical (systematically named λ3-ethyne and hydridodicarbon(CC)) is an organic compound with the chemical formula C≡CH (also written [CCH] or C
2
H
). It is a simple molecule that does not occur naturally on Earth but is abundant in the interstellar medium. It was first observed by electron spin resonance isolated in a solid argon matrix at liquid helium temperatures in 1963 by Cochran and coworkers at the Johns Hopkins Applied Physics Laboratory. It was first observed in the gas phase by Tucker and coworkers in November 1973 toward the Orion Nebula, using the NRAO 11-meter radio telescope. It has since been detected in a large variety of interstellar environments, including dense molecular clouds, bok globules, star forming regions, the shells around carbon-rich evolved stars, and even in other galaxies.

The hexatriynyl radical, C6H, is an organic radical molecule consisting of a linear chain of six carbon atoms terminated by a hydrogen. The unpaired electron is located at the opposite end to the hydrogen atom, as indicated. Both experimental work and computer simulations on this species was done in the early 1990s.

<span class="mw-page-title-main">Helium hydride ion</span> Chemical compound

The helium hydride ion, 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.

<span class="mw-page-title-main">Dihydrogen cation</span> Molecular ion

The dihydrogen cation or hydrogen molecular ion is a cation with formula H+
2
. It consists of two hydrogen nuclei (protons), each sharing a single electron. It is the simplest molecular ion.

<span class="mw-page-title-main">Protonated hydrogen cyanide</span> Chemical compound

HCNH+, also known as protonated hydrogen cyanide, is a molecular ion of astrophysical interest. It also exists in the condensed state when formed by superacids.

<span class="mw-page-title-main">Cyano radical</span> Chemical compound

The cyano radical (or cyanido radical) is a radical with molecular formula CN, sometimes written CN. The cyano radical was one of the first detected molecules in the interstellar medium, in 1938. Its detection and analysis was influential in astrochemistry. The discovery was confirmed with a coudé spectrograph, which was made famous and credible due to this detection. ·CN has been observed in both diffuse clouds and dense clouds. Usually, CN is detected in regions with hydrogen cyanide, hydrogen isocyanide, and HCNH+, since it is involved in the creation and destruction of these species (see also Cyanogen).

Triatomic hydrogen or H3 is an unstable triatomic molecule containing only hydrogen. Since this molecule contains only three atoms of hydrogen it is the simplest triatomic molecule and it is relatively simple to numerically solve the quantum mechanics description of the particles. Being unstable the molecule breaks up in under a millionth of a second. Its fleeting lifetime makes it rare, but it is quite commonly formed and destroyed in the universe thanks to the commonness of the trihydrogen cation. The infrared spectrum of H3 due to vibration and rotation is very similar to that of the ion, H+
3
. In the early universe this ability to emit infrared light allowed the primordial hydrogen and helium gas to cool down so as to form stars.

<span class="mw-page-title-main">Magnesium monohydride</span> Chemical compound

Magnesium monohydride is a molecular gas with formula MgH that exists at high temperatures, such as the atmospheres of the Sun and stars. It was originally known as magnesium hydride, although that name is now more commonly used when referring to the similar chemical magnesium dihydride.

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 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.

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.

References

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