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Helium hydride ion - Wikipedia https://en.wikipedia.org/wiki/Helium_hydride_ion
+
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]
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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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:
The dihelium hydride cation, He2H+, is formed by the reaction of dihelium cation with molecular hydrogen:
He+2 + H2 → He2H+ + H
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
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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Helium hydride ion - Wikipedia https://en.wikipedia.org/wiki/Helium_hydride_ion
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
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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References
1. "hydridohelium(1+) (CHEBI:33688)" (https://www.ebi.ac.uk/chebi/searchId.do?chebiId=33688). Chemical
Entities of Biological Interest (ChEBI). European Bioinformatics Institute.
2. Krzysztof Pachucki and Jacek Komasa (2012): "", Journal of Chemical Physics, volume 137, issue 20, article
204314. doi:10.1063/1.4768169 (https://doi.org/10.1063%2F1.4768169)
3. "Hydridohelium (CHEBI:33689)" (https://www.ebi.ac.uk/chebi/searchId.do?chebiId=CHEBI%3A33689).
Chemical Entities of Biological Interest (ChEBI). European Bioinformatics Institute.
4. Hogness, T. R.; Lunn, E. G. (1925). "The Ionization of Hydrogen by Electron Impact as Interpreted by Positive
Ray Analysis". Physical Review. 26 (1): 44–55. Bibcode:1925PhRv...26...44H (http://adsabs.harvard.edu
/abs/1925PhRv...26...44H). doi:10.1103/PhysRev.26.44 (https://doi.org/10.1103%2FPhysRev.26.44).
5. Coxon, J.; Hajigeorgiou, P. G. (1999). "Experimental Born–Oppenheimer Potential for the X1Σ+ Ground State
of HeH+: Comparison with the Ab Initio Potential". Journal of Molecular Spectroscopy. 193 (2): 306–318.
Bibcode:1999JMoSp.193..306C (http://adsabs.harvard.edu/abs/1999JMoSp.193..306C).
doi:10.1006/jmsp.1998.7740 (https://doi.org/10.1006%2Fjmsp.1998.7740). PMID 9920707
(https://www.ncbi.nlm.nih.gov/pubmed/9920707).
6. Dias, A. M. (1999). "Dipole Moment Calculation to Small Diatomic Molecules: Implementation on a Two-
Electron Self-Consistent-Field ab initio Program" (https://ned.unifenas.br/amdias/wp-admin/apostilas/hf1s.pdf)
(PDF). Rev da Univ de Alfenas. 5 (1): 77–79.
7. Engel, Elodie A.; Doss, Natasha; Harris, Gregory J.; Tennyson, Jonathan (2005). "Calculated spectra for
HeH+ and its effect on the opacity of cool metal-poor stars". Monthly Notices of the Royal Astronomical
Society. 357 (2): 471–477. arXiv:astro-ph/0411267 (https://arxiv.org/abs/astro-ph/0411267).
Bibcode:2005MNRAS.357..471E (http://adsabs.harvard.edu/abs/2005MNRAS.357..471E).
doi:10.1111/j.1365-2966.2005.08611.x (https://doi.org/10.1111%2Fj.1365-2966.2005.08611.x).
8. Coyne, John P.; Ball, David W. (2009). "Alpha particle chemistry. On the formation of stable complexes
between He2+ and other simple species: implications for atmospheric and interstellar chemistry". Journal of
Molecular Modeling. 15 (1): 35–40. doi:10.1007/s00894-008-0371-3 (https://doi.org
/10.1007%2Fs00894-008-0371-3). PMID 18936986 (https://www.ncbi.nlm.nih.gov/pubmed/18936986).
9. Murray Cantwell (1956): "Molecular Excitation in Beta Decay". Physical Reviews, volume 101, issue 6, pages
1747-1756.doi:10.1103/PhysRev.101.1747 (https://doi.org/10.1103%2FPhysRev.101.1747).
10. Wei-Cheng Tung, Michele Pavanello, and Ludwik Adamowicz (2012): "Accurate potential energy curves for
HeH+ isotopologues ". Journal of Chemical Physics, volume 137, issue 16, pages 164305.
doi:10.1063/1.4759077 (https://doi.org/10.1063%2F1.4759077)
11. H. M. Schwartz (1955): "Excitation of Molecules in the Beta Decay of a Constituent Atom". Journal of
Chemical Physics, volume 23, pages 400-401. doi:10.1063/1.1741982 (https://doi.org
/10.1063%2F1.1741982).
12. Arthur H. Snell, Frances Pleasonton, H. E. Leming (1957): "Molecular dissociation following radioactive decay:
Tritium hydride". Journal of Inorganic and Nuclear Chemistry, volume 5, issue 2, pages 112-117.
doi:10.1016/0022-1902(57)80051-7 (https://doi.org/10.1016%2F0022-1902%2857%2980051-7)
13. Kenneth T. Bainbridge (1933): "Comparison of the Masses of H2 and Helium". Physical Reviews, volume 44,
issue 1, page 57. doi:10.1103/PhysRev.44.57 (https://doi.org/10.1103%2FPhysRev.44.57)
14. P. Bernath and T. Amano (1982): "Detection of the Infrared Fundamental Band of HeH+". Physical Review
Letters, volume 48, issue 1, pages 20-22. doi:10.1103/PhysRevLett.48.20 (https://doi.org
/10.1103%2FPhysRevLett.48.20)
15. Möller, Thomas; Beland, Michael; Zimmerer, Georg (1985). "Observation of Fluorescence of the HeH
Molecule". Physical Review Letters. 55 (20): 2145–2148. Bibcode:1985PhRvL..55.2145M
(http://adsabs.harvard.edu/abs/1985PhRvL..55.2145M). doi:10.1103/PhysRevLett.55.2145 (https://doi.org
/10.1103%2FPhysRevLett.55.2145). PMID 10032060 (https://www.ncbi.nlm.nih.gov/pubmed/10032060).
16. "Wolfgang Ketterle: The Nobel Prize in Physics 2001" (http://nobelprize.org/nobel_prizes/physics/laureates
/2001/ketterle-autobio.html).
5 of 7 4/23/2019, 12:33 PM
Helium hydride ion - Wikipedia https://en.wikipedia.org/wiki/Helium_hydride_ion
17. Ketterle, W.; Figger, H.; Walther, H. (1985). "Emission spectra of bound helium hydride". Physical Review
Letters. 55 (27): 2941–2944. Bibcode:1985PhRvL..55.2941K (http://adsabs.harvard.edu
/abs/1985PhRvL..55.2941K). doi:10.1103/PhysRevLett.55.2941 (https://doi.org
/10.1103%2FPhysRevLett.55.2941). PMID 10032281 (https://www.ncbi.nlm.nih.gov/pubmed/10032281).
18. Grandinetti, Felice (October 2004). "Helium chemistry: a survey of the role of the ionic species". International
Journal of Mass Spectrometry. 237 (2–3): 243–267. Bibcode:2004IJMSp.237..243G
(http://adsabs.harvard.edu/abs/2004IJMSp.237..243G). doi:10.1016/j.ijms.2004.07.012 (https://doi.org
/10.1016%2Fj.ijms.2004.07.012).
19. Cacace, Fulvio (1970). Gaseous Carbonium Ions from the Decay of Tritiated Molecules. Advances in Physical
Organic Chemistry. 8. pp. 79–149. doi:10.1016/S0065-3160(08)60321-4 (https://doi.org
/10.1016%2FS0065-3160%2808%2960321-4). ISBN 9780120335084.
20. Lias, S. G.; Liebman, J. F.; Levin, R. D. (1984). "Evaluated Gas Phase Basicities and Proton Affinities of
Molecules; Heats of Formation of Protonated Molecules". Journal of Physical and Chemical Reference Data.
13 (3): 695. Bibcode:1984JPCRD..13..695L (http://adsabs.harvard.edu/abs/1984JPCRD..13..695L).
doi:10.1063/1.555719 (https://doi.org/10.1063%2F1.555719).
21. Carrington, Alan; Gammie, David I.; Shaw, Andrew M.; Taylor, Susie M.; Hutson, Jeremy M. (1996).
+
"Observation of a microwave spectrum of the long-range He⋯H2 complex". Chemical Physics Letters. 260
(3–4): 395–405. Bibcode:1996CPL...260..395C (http://adsabs.harvard.edu/abs/1996CPL...260..395C).
doi:10.1016/0009-2614(96)00860-3 (https://doi.org/10.1016%2F0009-2614%2896%2900860-3).
22. Pauzat, F.; Ellinger, Y. (2005). "Where do noble gases hide in space?". In Markwick-Kemper, A. J. (ed.).
Astrochemistry: Recent Successes and Current Challenges (https://web.archive.org/web/20070202203834
/http://asilomar.caltech.edu/abstracts_processed/Pauzat_2z6IeIOR.pdf) (PDF). Poster Book IAU Symposium
No. 231. 231. Bibcode:2005IAUS..231.....L (http://adsabs.harvard.edu/abs/2005IAUS..231.....L). Archived
from the original (http://asilomar.caltech.edu/abstracts_processed/Pauzat_2z6IeIOR.pdf) (PDF) on
2007-02-02.
23. J. Y. Beach (1936): "Quantum-Mechanical Treatment of Helium Hydride Molecule-Ion HeH+". Journal of
Chemical Physics, volume 4, issue 6, pages 353-357. doi:10.1063/1.1749857 (https://doi.org
/10.1063%2F1.1749857)
24. Sôroku Toh (1940): "Quantum-Mechanical Treatment of Helium-Hydride Molecule Ion HeH+". Proceedings of
the Physico-Mathematical Society of Japan, 3rd Series, volume 22, issue 2, pages 119-126.
doi:10.11429/ppmsj1919.22.2_119 (https://doi.org/10.11429%2Fppmsj1919.22.2_119).
25. Arthur A. Evett (1956): "Ground State of the Helium-Hydride Ion". Journal of Chemical Physics, volume 24,
issue 1, pages 150-152. doi:10.1063/1.1700818 (https://doi.org/10.1063%2F1.1700818)
26. V. A. Lubimov, E. G. Novikov, V. Z. Nozik, E. F. Tretyakov, V. S. Kosik (1980): "An estimate of the νe mass from
the β-spectrum of tritium in the valine molecule", Physics Letters B, volume 94, issue 2, pages 266-268.
doi:10.1016/0370-2693(80)90873-4 (https://doi.org/10.1016%2F0370-2693%2880%2990873-4).
27. Cite error: The named reference fack1985 was invoked but never defined (see the help page).
28. David E. Tolliver, George A. Kyrala, and William H. Wing (1979): "Observation of the Infrared Spectrum of the
4
Helium-Hydride Molecular Ion [ HeH]+". Physical Review Letters, volume 43, issue 23, pages 1719-1722.
doi:10.1103/PhysRevLett.43.1719 (https://doi.org/10.1103%2FPhysRevLett.43.1719)
29. Fernández, J.; Martín, F. (2007). "Photoionization of the HeH+ molecular ion". Journal of Physics B. 40 (12):
2471–2480. Bibcode:2007JPhB...40.2471F (http://adsabs.harvard.edu/abs/2007JPhB...40.2471F).
doi:10.1088/0953-4075/40/12/020 (https://doi.org/10.1088%2F0953-4075%2F40%2F12%2F020).
30. Stutzki, Jürgen; Risacher, Christophe; Ricken, Oliver; Klein, Bernd; Karl Jacobs; Graf, Urs U.; Menten, Karl
M.; Neufeld, David; Wiesemeyer, Helmut (April 2019). "Astrophysical detection of the helium hydride ion
HeH+". Nature. 568 (7752): 357. doi:10.1038/s41586-019-1090-x (https://doi.org
/10.1038%2Fs41586-019-1090-x). PMID 30996316 (https://www.ncbi.nlm.nih.gov/pubmed/30996316).
31. Mannone, F., ed. (1993). Safety in Tritium Handling Technology. Springer. p. 92.
doi:10.1007/978-94-011-1910-8_4 (https://doi.org/10.1007%2F978-94-011-1910-8_4).
ISBN 978-94-011-1910-8.
6 of 7 4/23/2019, 12:33 PM
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32. Liu, X.-W.; Barlow, M. J.; Dalgarno, A.; Tennyson, J.; Lim, T.; Swinyard, B. M.; Cernicharo, J.; Cox, P.;
Baluteau, J.-P.; Pequignot, D.; Nguyen, Q. R.; Emery, R. J.; Clegg, P. E. (1997). "An ISO Long Wavelength
Spectrometer detection of CH in NGC 7027 and an HeH+ upper limit". Monthly Notices of the Royal
Astronomical Society. 290 (4): L71–L75. Bibcode:1997MNRAS.290L..71L (http://adsabs.harvard.edu
/abs/1997MNRAS.290L..71L). doi:10.1093/mnras/290.4.l71 (https://doi.org/10.1093%2Fmnras%2F290.4.l71).
33. Harris, G. J.; Lynas-Gray, A. E.; Miller, S.; Tennyson, J. (2004). "The Role of HeH+ in Cool Helium-rich White
Dwarfs". The Astrophysical Journal. 617 (2): L143–L146. arXiv:astro-ph/0411331 (https://arxiv.org/abs/astro-
ph/0411331). Bibcode:2004ApJ...617L.143H (http://adsabs.harvard.edu/abs/2004ApJ...617L.143H).
doi:10.1086/427391 (https://doi.org/10.1086%2F427391).
34. Roberge, W.; Delgarno, A. (1982). "The formation and destruction of HeH+ in astrophysical plasmas". The
Astrophysical Journal. 255: 489–496. Bibcode:1982ApJ...255..489R (http://adsabs.harvard.edu
/abs/1982ApJ...255..489R). doi:10.1086/159849 (https://doi.org/10.1086%2F159849).
35. Neufeld, David A.; Dalgarno, A. (1989). "Fast molecular shocks. I – Reformation of molecules behind a
dissociative shock". Astrophysical Journal. 340: 869–893. Bibcode:1989ApJ...340..869N
(http://adsabs.harvard.edu/abs/1989ApJ...340..869N). doi:10.1086/167441 (https://doi.org
/10.1086%2F167441).
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