Helium hydride ion - Wikipedia https://en.wikipedia.

org/wiki/Helium_hydride_ion

Helium hydride ion

The helium hydride ion or hydridohelium(1+) ion is a
Helium hydride ion
cation (positively charged ion) with chemical formula HeH+.
It consists of a helium atom bonded to a hydrogen atom, with
one electron removed. It is the lightest heteronuclear ion, and
is believed to be one of the first compounds formed in the
universe after the big bang.[2]

The ion was first produced in a laboratory in 1925. It is stable

in isolation, but extremely reactive, and cannot be prepared
in bulk because it would react with any other molecule it
came in contact with. Noted as the strongest known acid, its
occurrence in the interstellar medium has been conjectured
since the 1970s,[3] and it was finally detected in April 2019.[4]
Names
Systematic IUPAC name
Hydridohelium(1+)[1]
Contents Identifiers
Physical properties 3D model Interactive image
Isotopologues (JSmol) (https://chemapps.stolaf.edu
Neutral molecule
/jmol/jmol.php?model=%5BHeH
Chemical properties and reactions
%2B%5D)
Preparation
Acidity ChEBI CHEBI:33688
Other helium-hydrogen ions (https://www.ebi.ac.uk/chebi
History /searchId.do?chebiId=33688)
Natural occurrence CHEBI:33689
From decay of tritium (https://www.ebi.ac.uk/chebi
Interstellar medium /searchId.do?chebiId=33689)
References neutral excimer
ChemSpider 21106447
(http://www.chemspider.com
Physical properties /Chemical-
The helium hydrogen ion is isoelectronic with molecular Structure.21106447.html)
hydrogen (H2).[4] Gmelin 2
Reference
Unlike the dihydrogen ion H+
2 , the helium hydride ion has a
InChI
permanent dipole moment, which makes its spectroscopic
characterization easier.[5] The calculated dipole moment of SMILES
HeH+ is 2.26 or 2.84 D.[6] However, one of its most Properties
prominent spectral lines, at 149.14 µm, coincides with a +
Chemical HeH
doublet of spectral lines belonging to the methylidyne radical formula
⫶CH.[7] Molar mass 5.01054 g·mol−1

The length of the covalent bond in the ion is 0.772 Å.[8]

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Isotopologues Conjugate Helium

base
The helium hydride ion has six relatively stable
isotopologues, that differ in the isotopes of the two elements, Except where otherwise noted, data are given
for materials in their standard state (at 25 °C
and hence in the total atomic mass number (A) and the total
[77 °F], 100 kPa).
number of neutrons (N) in the two nuclei:
Infobox references
3 1 3
[ He H]+ or [ HeH]+ (A = 4, N = 1) [9][10]
3 2 3
[ He H]+ or [ HeD]+ (A = 5, N = 2) [9][10]
3 3 3
[ He H]+ or [ HeT]+ (A = 6, N = 3; radioactive) [11][9][12]
4 1 4
[ He H]+ or [ HeH]+ (A = 5, N = 2) [4][13][14][2][10]
4 2 4
[ He H]+ or [ HeD]+ (A = 6, N = 3) [13][10]
4 3 4
[ He H]+ or [ HeT]+ (A = 7, N = 4; radioactive)
They all have three protons and two electrons. The first three are generated by radioactive decay of tritium in the
1 3 2 3 3
molecules HT = H H, DT = H H, and T2 = H2, respectively. The last three can be generated by ionizing the
appropriate isotopologue of H2 in the presence of helium-4.[4]

+
The following isotopologues of the helium hydride ion, of the dihydrogen ion H2, and of the trihydrogen ion H3
have the same total atomic mass number A:

3
[ HeH]+, [D2]+, [TH]+, [DH2]+ (A = 4)
3 4
[ HeD]+, [ HeH]+, [DT]+, [TH2]+, [D2H]+ (A = 5)
3 4
[ HeT]+, [ HeD]+, [T2]+, [TDH]+, [D3]+ (A = 6)
4
[ HeT]+, [TD2]+, [T2H]+ (A = 7)
The masses in each row above are not equal, though, because the binding energies in the nuclei are different.[13]

Neutral molecule
Unlike the helium hydride ion, the neutral helium hydride molecule HeH is not stable in the ground state.
However, it does exist in an excited state as an excimer (HeH*), and its spectrum was first observed in the mid
1980s.[15][16][17]

The neutral molecule is the first entry in the Gmelin database.[3]

Chemical properties and reactions

Preparation
Since HeH+ cannot be stored in any usable form, its chemistry must be studied by forming it in situ.

Reactions with organic substances, for example, can be studied by creating a tritium derivative of the desired
organic compound. Decay of tritium to 3He+ followed by its extraction of a hydrogen atom yields 3HeH+ which is
then surrounded by the organic material and will in turn react.[18][19]

Acidity
HeH+ cannot be prepared in a condensed phase, as it would donate a proton to any anion, molecule or atom that it
came in contact with. It has been shown to protonate O2, NH3, SO2, H2O, and CO2, giving O2H+, NH+ +
4 , HSO2 ,

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H3O+, and HCO+ 2.

[18] Other molecules such as nitric oxide, nitrogen dioxide, nitrous oxide, hydrogen sulfide,

methane, acetylene, ethylene, ethane, methanol and acetonitrile react but break up due to the large amount of
energy produced.[18]

In fact, HeH+ is the strongest known acid, with a proton affinity of 177.8 kJ/mol.[20] The hypothetical aqueous
acidity can be estimated using Hess's law:

HeH+(g) → H+(g) + He(g) +178 kJ/mol [20]

HeH+(aq) → HeH+(g) +973 kJ/mol (a)
H+(g) → H+(aq) −1530 kJ/mol
He(g) → He(aq) +19 kJ/mol (b)
+ +
HeH (aq) → H (aq) + He(aq) −360 kJ/mol

(a) Estimated to be same as for Li+(aq) → Li+(g).

(b) Estimated from solubility data.

A free energy change of dissociation of −360 kJ/mol is equivalent to a pKa of −63.

Other helium-hydrogen ions

Additional helium atoms can attach to HeH+ to form larger clusters such as He2H+, He3H+, He4H+, He5H+ and
He6H+.[18]

The dihelium hydride cation, He2H+, is formed by the reaction of dihelium cation with molecular hydrogen:

He+2 + H2 → He2H+ + H

It is a linear ion with hydrogen in the centre.[18]

The hexahelium hydride ion, He6H+, is particularly stable.[18]

Other helium hydride ions are known or have been studied theoretically. Helium dihydride ion, or
dihydridohelium(1+), HeH+
2 , has been observed using microwave spectroscopy.
[21] It has a calculated binding

energy of 25.1 kJ/mol, while trihydridohelium(1+), HeH+

3 , has a calculated binding energy of 0.42 kJ/mol.
[22]

History
4 1
Hydridohelium(1+), specifically [ He H]+, was first detected indirectly in 1925 by T. R. Hogness and E. G. Lunn.
They were injecting protons of known energy into a rarefied mixture of hydrogen and helium, in order to study the
+
formation of hydrogen ions like H , H+ + +
2 and H3 . They observed that H3 appeared at the same beam energy (16 eV)
as H+
2 , and its concentration increased with pressure much more than that of the other two ions. From this data,
they concluded that the H+ 2 ions were transferring a proton to molecules that they collided with, including
helium.[4]

4 1
In 1933, K. Bainbridge used mass spectrometry to compare the masses of the ions [ He H]+ (helium hydride ion)
2 1
and [ H2 H]+ (twice-deuterated trihydrogen ion) in order to obtain an accurate measurement of the atomic mass of
4
deuterium relative to that of helium. Both ions have 3 protons, 2 neutrons, and 2 electrons. He also compared [ He
2 2
H]+ (helium deuteride ion) with [ H3]+ (trideuterium ion), both with 3 protons and 3 neutrons.[13]

4 1
The first attempt to compute the structure of the HeH+ ion (specifically, [ He H]+) by quantum mechanical theory

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was made by J. Beach in 1936.[23] Improved computations were sporadically published over the next decades.[24]
[25]

3
H. Schwartz observed in 1955 that the decay of the tritium molecule T2 = H2 should generate the helium hydride
3
ion [ HeT]+ with high probability. In 1980, V. Lubimov (Lyubimov) at the ITEP laboratory in Moscow claimed to
have detected a significant rest mass (30 ± 16) eV for the neutrino, by analyzing the energy spectrum of the β decay
of tritium.[26] The claim was disputed, and several other groups set out to check it by studying the decay of
molecular tritium T2. It was known that some of the energy released by that decay would be diverted to the
3
excitation of the decay products, including [ HeT]+; and this phenomenon could be a significant source of error in
that experiment. This observation motivated numerous efforts to precisely compute the expected energy states of
that ion in order to reduce the uncertainty of those measurements.[27] Many have improved the computations
since then, and now there is quite good agreement between computed and experimental properties; including for
4 2 3 1 3 2
the isotopologues [ He H]+, [ He H]+, and [ He H]+.[2][10]

In 1956, M. Cantwell predicted theoretically that the spectrum of vibrations of that ion should be observable in the
3 3 1
infrared; and the spectra of the deuterium and common hydrogen isotopologues ([ HeD]+ and [ He H]+) should
4 1
lie closer to visible light and hence easier to observe.[9] The first detection of the spectrum of [ He H]+ was made
by D. Tolliver and others in 1979, at wavenumbers between 1700 and 1900 cm−1.[28] In 1982, P. Bernath and T.
Amano detected nine infrared lines between 2164 and 3158 waves per cm.[14]

HeH+ has long been conjectured since the 1970s to exist in the interstellar medium.[29] Its first detection, in the
nebula NGC 7027, was reported in an article published in the journal Nature in April 2019.[30]

Natural occurrence

From decay of tritium

The helium hydride ion is formed during the decay of tritium in the molecule HT or tritium molecule T2. Although
excited by the recoil from the beta decay, the molecule remains bound together.[31]

Interstellar medium
It is believed to be the first compound to have formed in the universe,[7] and is of fundamental importance in
understanding the chemistry of the early universe.[32] This is because hydrogen and helium were almost the only
types of atoms formed in Big Bang nucleosynthesis. Stars formed from the primordial material should contain
HeH+, which could influence their formation and subsequent evolution. In particular, its strong dipole moment
makes it relevant to the opacity of zero-metallicity stars.[7] HeH+ is also thought to be an important constituent of
the atmospheres of helium-rich white dwarfs, where it increases the opacity of the gas and causes the star to cool
more slowly.[33]

Several locations have been suggested as possible places HeH+ might be detected. These include cool helium
stars,[7] H II regions,[34] and dense planetary nebulae[34] like NGC 7027.[32]

HeH+ could be formed in the cooling gas behind dissociative shocks in dense interstellar clouds, such as the shocks
caused by stellar winds, supernovae and outflowing material from young stars. If the speed of the shock is greater
than about 90 kilometres per second (56 mi/s), quantities large enough to detect might be formed. If detected, the
emissions from HeH+ would then be useful tracers of the shock.[35]

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