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Helium hydride ion

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Helium hydride ion

Helium hydride ion
Spacefill model of the helium hydride ion
Ball and stick model of the helium hydride ion
Identifiers
ChemSpider  YesY
ChEBI
Gmelin Reference 2
Jmol-3D images Image 1
Properties
Molecular formula HeH+
Molar mass 5.01054 g mol-1
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)

The hydrohelium(1+) cation, HeH+, also known as the helium hydride ion or helium-hydride molecular ion, is a positively charged ion formed by the reaction of a proton with a helium atom in the gas phase, first produced in the laboratory in 1925 and isoelectronic with molecular hydrogen.[2] It is the strongest known acid, with a proton affinity of 177.8 kJ/mol.[3] It has been suggested that HeH+ should occur naturally in the interstellar medium, but it has not yet been detected.[4] It is the simplest heteronuclear ion, and is comparable with the hydrogen molecular ion, H+
2
. Unlike H+
2
, however, it has a permanent dipole moment, which makes its spectroscopic characterization easier.[5]

Properties

HHe+ cannot be prepared in a condensed phase, as it would protonate any anion, molecule or atom with which it were associated. However it is possible to estimate a hypothetical aqueous acidity using Hess's law:

HHe+(g) H+(g) + He(g) +178 kJ/mol [3]
HHe+(aq) HHe+(g)   +973 kJ/mol [6]
H+(g) H+(aq)   – 1530 kJ/mol  
He(g) He(aq)   +19 kJ/mol [7]
HHe+(aq) H+(aq) + He(aq) – 360 kJ/mol  

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

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

Other helium hydride ions are known or have been studied theoretically. HeH+
2
, which has been observed using microwave spectroscopy,[9] has a calculated binding energy of 25.1 kJ/mol, while HeH+
3
has a calculated binding energy of 0.42 kJ/mol.[10]

Natural occurrence

The helium hydride ion is formed during the decay of tritium in the HT or tritium molecule T2. Although excited by the recoil from the beta decay the molecule remains bound together.[11]

HeH+ is thought to exist in the interstellar medium, although it has not yet been unambiguously detected.[12] It is believed to be the first compound to have formed in the universe,[12] and is of fundamental importance in understanding the chemistry of the early universe.[13] 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.[12] 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.[14]

Several locations have been suggested as possible places HeH+ might be detected. These include cool helium stars,[12] H II regions,[15] and dense planetary nebulae[15] (in particular NGC 7027).[13] Detecting HeH+ spectroscopically is complicated by the fact that one of its most prominent spectral lines, at 149.14 μm, coincides with a doublet of spectral lines belonging to the methylidyne radical CH.[12]

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 km/s, quantities large enough to detect might be formed. If detected, the emissions from HeH+ would then be useful tracers of the shock.[16]

Neutral molecule

Unlike the helium hydride ion, the neutral helium hydride molecule is not stable in the ground state. However, it does exist in an excited state as an excimer, and its spectrum was first observed in the mid 1980s.[17][18][19]

References and notes

Unless otherwise stated, numerical data are taken from Weast, R. C. (Ed.) (1981). CRC Handbook of Chemistry and Physics (62nd Edn.). Boca Raton, FL: CRC Press. ISBN 0-8493-0462-8.

  1. ^ "hydridohelium(1+) (CHEBI:33688)". Chemical Entities of Biological Interest (ChEBI). UK: European Bioinformatics Institute. 
  2. ^ T. R. Hogness and E. G. Lunn (1925). "The Ionization of Hydrogen by Electron Impact as Interpreted by Positive Ray Analysis".  
  3. ^ a b Lias, S. G.; Liebman, J. F.; Levin, R. D.; Liebman; Levin (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.  
  4. ^ J. Fernandez; F. Martin; Martín (2007). "Photoionization of the HeH+ molecular ion". J. Phys. B: At. Mol. Opt. Phys 40 (12): 2471–2480.  
  5. ^ Coxon, J; Hajigeorgiou, PG (1999). "Experimental Born–Oppenheimer Potential for theX1Σ+Ground State of HeH+: Comparison with theAb InitioPotential". Journal of Molecular Spectroscopy 193 (2): 306–318.  
  6. ^ Estimated to be the same as for Li+(aq) → Li+(g).
  7. ^ Estimated from solubility data.
  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.  
  9. ^ Alan Carrington, David I. Gammie, Andrew M. Shaw, Susie M. Taylor and Jeremy M. Hutson (1996). "Observation of a microwave spectrum of the long-range He···H2+ complex". Chemical Physics Letters 260 (3–4): 395–405.  
  10. ^ F.Pauzat and Y. Ellinger Where do noble gases hide in space?, Astrochemistry: Recent Successes and Current Challenges, Poster Book IAU Symposium No. 231, 2005 A. J. Markwick-Kemper (ed.)
  11. ^ F Mannone: Safety in Tritium Handling Technology Springer 1993, p 92
  12. ^ a b c d e 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.  
  13. ^ a b Liu, X.-W.; Barlow; Dalgarno; Tennyson; Lim; Swinyard; Cernicharo; Cox; Baluteau; Barlow, M. J.; Dalgarno, A.; Tennyson, J.; Lim, T.; Swinyard, B. M.; Cernicharo, J.; Cox, P.; Baluteau, J.-P.; Pequignot, D.; Nguyen-Q-Rieu; 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.  
  14. ^ Harris, G.J.; Lynas-Gray, A.E.; Miller, S.; Tennyson, J. (2004). "The Role of HeH+ in Cool Helium-rich White Dwarfs".  
  15. ^ a b Roberge, W.; Delgarno, A. (1982). "The formation and destruction of HeH/+/ in astrophysical plasmas".  
  16. ^ Neufeld, David A.; Dalgarno, A. (1989). "Fast molecular shocks. I – Reformation of molecules behind a dissociative shock".  
  17. ^ Thomas Möller, Michael Beland, and Georg Zimmerer (1985). "Observation of Fluorescence of the HeH Molecule". Phys. Rev. Lett. 55 (20): 2145–2148.  
  18. ^ Wolfgang Ketterle, The Nobel Prize in Physics 2001
  19. ^ W. Ketterle, H. Figger, and H. Walther (1985). "Emission spectra of bound helium hydride". Phys. Rev. Lett. 55 (27): 2941–2944.  
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