Calcium monohydride

Last updated
Calcium monohydride
Calcium Monohydride.svg
Calcium-monohydride-3D-vdW.png
Names
IUPAC name
Calcium monohydride
Other names
Calcium(I) hydride
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
  • InChI=1S/Ca.2H/q+1;;-1 X mark.svgN
    Key: CHYDSHXOJGDCRJ-UHFFFAOYSA-N X mark.svgN
  • InChI=1S/Ca.H
    Key: PKHCKQOIOXDRJH-UHFFFAOYSA-N
  • [H].[Ca]
Properties
CaH
Molar mass 41.085899 g/mol
Appearanceglowing red gas
reacts violently
Related compounds
Other cations
Beryllium monohydride,
Magnesium monohydride,
Strontium monohydride,
Barium monohydride,
Potassium hydride
Related calcium hydrides
Calcium hydride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Calcium monohydride is a molecule composed of calcium and hydrogen with formula CaH. It can be found in stars as a gas formed when calcium atoms are present with hydrogen atoms.

Contents

Discovery

Calcium monohydride was first discovered when its spectrum was observed in Alpha Herculis and ο Ceti by Alfred Fowler in 1907. [1] [2] It was observed in sunspots the following year by C. M. Olmsted. [3] [4] Next, it was made in a laboratory in 1909 by A. Eagle, [3] and with early research by Hulthèn, [5] and Watson and Weber in 1935. [6] It was further observed in red dwarfs by Y. Öhman in 1934. Öhman proposed its use as a proxy for stellar luminosity, similar to magnesium monohydride (MgH), in being more apparent in the spectra of compact, cool, high surface gravity stars such as M dwarfs than in cool, low surface gravity stars such as M giants of non-negligible, or even comparable, metallicity. [7]

Calcium monohydride is the first molecular gas that was cooled by a cold buffer gas and then trapped by a magnetic field. This extends the study of trapped cold atoms such as rubidium to molecules. [8]

Formation

Calcium monohydride can be formed by exposing metallic calcium to an electric discharge in a hydrogen atmosphere above 750 °C. Below this temperature the hydrogen is absorbed to form calcium hydride. [3]

Calcium monohydride can be formed by laser ablation of calcium dihydride in a helium atmosphere. [9]

Gaseous calcium reacts with formaldehyde at temperatures around 1200 K to make CaH as well as some CaOH and CaO. This reaction glows orange-red.

Properties

The dipole moment of the CaH molecule is 2.94 debye. [10] [11] Spectrographic constants have been measured as bond length Re=2.0025 Å dissociation energy De=1.837 eV and harmonic vibrational frequency ωe=1298.34 cm−1. [10] Ionisation potential is 5.8 eV. [10] Electron affinity is 0.9 eV. [10]

The ground state is X2Σ+. [10]

The electronic states are: [12]

Spectrum

B2Σ, with ν'=0 ← X2Σ with ν"=0 634 nm (or is it 690 nm?) [14] CaH fluoresces with 634 nm light giving 690 nm emissions. [9]

B2Σ+ ← X2Σ+ 585.8 nm to 590.2 nm. [15]

A+2Π ← X2Σ+ 686.2 to 697.8 nm [15]

R12 branch [15]

J'J"N"νnmTHz
3/21/2014408.94694.0135431.9691
5/23/2114421.12693.4274432.3343
7/25/2214432.92692.8605432.6881
9/27/2314444.54692.3031433.0364
11/29/2414455.76691.7658433.3728
13/211/2514467.20691.2188433.71574

R2 branch [15]

J'J"N"νnmTHz
3/21/2014480.93690.5633434.1274
5/23/2114495.08689.8893434.5516
7/25/2214510.09689.1756435.0015
9/27/2314525.53688.4430435.4644
11/29/2414541.43687.6903435.9411
13/211/2514557.98686.9085436.4373

C2Σ+ →X2Σ+ transition is in near ultraviolet. [3]

Microwave spectrum

The energy required to spin the CaH molecule from its lowest level to the first quantum level corresponds to a microwave frequency, so there is an absorption around 253 GHz. However, the spin of the molecule is also affected by the spin of an unpaired electron on the calcium, and the spin of the proton in the hydrogen. The electron spin leads to splitting of the line by about 1911.7 MHz, and the spin relative to the proton spin results in hyperfine splitting of the line by about 157.3 MHz. [16]

molecule spin
quantum number
electron spin
quantum number
proton spin
quantum number
frequency
NN'JJ'FF'kHz
011/21/211252163082
011/21/210252216347
011/21/201252320467
011/23/211254074834
011/23/212254176415
011/23/201254232179

Reactions

CaH reacts with Lithium as a cold gas releasing 0.9eV of energy and forming LiH molecules and calcium atoms. [17]

Extra reading

Related Research Articles

<span class="mw-page-title-main">Spectroscopy</span> Study involving matter and electromagnetic radiation

Spectroscopy is the field of study that measures and interprets electromagnetic spectra. In narrower contexts, spectroscopy is the precise study of color as generalized from visible light to all bands of the electromagnetic spectrum.

<span class="mw-page-title-main">Spectral line</span> A distinctive narrow spectral feature of chemical species

A spectral line is a weaker or stronger region in an otherwise uniform and continuous spectrum. It may result 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.

<span class="mw-page-title-main">Rotational spectroscopy</span> Spectroscopy of quantized rotational states of gases

Rotational spectroscopy is concerned with the measurement of the energies of transitions between quantized rotational states of molecules in the gas phase. The rotational spectrum of polar molecules can be measured in absorption or emission by microwave spectroscopy or by far infrared spectroscopy. The rotational spectra of non-polar molecules cannot be observed by those methods, but can be observed and measured by Raman spectroscopy. Rotational spectroscopy is sometimes referred to as pure rotational spectroscopy to distinguish it from rotational-vibrational spectroscopy where changes in rotational energy occur together with changes in vibrational energy, and also from ro-vibronic spectroscopy where rotational, vibrational and electronic energy changes occur simultaneously.

<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.

In spectroscopy, a forbidden mechanism is a spectral line associated with absorption or emission of photons by atomic nuclei, atoms, or molecules which undergo a transition that is not allowed by a particular selection rule but is allowed if the approximation associated with that rule is not made. For example, in a situation where, according to usual approximations, the process cannot happen, but at a higher level of approximation the process is allowed but at a low rate.

In nuclear chemistry and nuclear physics, J-couplings are mediated through chemical bonds connecting two spins. It is an indirect interaction between two nuclear spins that arises from hyperfine interactions between the nuclei and local electrons. In NMR spectroscopy, J-coupling contains information about relative bond distances and angles. Most importantly, J-coupling provides information on the connectivity of chemical bonds. It is responsible for the often complex splitting of resonance lines in the NMR spectra of fairly simple molecules.

<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">Beryllium hydride</span> Chemical compound

Beryllium hydride is an inorganic compound with the chemical formula n. This alkaline earth hydride is a colourless solid that is insoluble in solvents that do not decompose it. Unlike the ionically bonded hydrides of the heavier Group 2 elements, beryllium hydride is covalently bonded.

<span class="mw-page-title-main">Nuclear magnetic resonance</span> Spectroscopic technique based on change of nuclear spin state

Nuclear magnetic resonance (NMR) is a physical phenomenon in which nuclei in a strong constant magnetic field are perturbed by a weak oscillating magnetic field and respond by producing an electromagnetic signal with a frequency characteristic of the magnetic field at the nucleus. This process occurs near resonance, when the oscillation frequency matches the intrinsic frequency of the nuclei, which depends on the strength of the static magnetic field, the chemical environment, and the magnetic properties of the isotope involved; in practical applications with static magnetic fields up to ca. 20 tesla, the frequency is similar to VHF and UHF television broadcasts (60–1000 MHz). NMR results from specific magnetic properties of certain atomic nuclei. Nuclear magnetic resonance spectroscopy is widely used to determine the structure of organic molecules in solution and study molecular physics and crystals as well as non-crystalline materials. NMR is also routinely used in advanced medical imaging techniques, such as in magnetic resonance imaging (MRI). The original application of NMR to condensed matter physics is nowadays mostly devoted to strongly correlated electron systems. It reveals large manybody couplings by fast broadband detection and it should not to be confused with solid state NMR, which aims at removing the effect of the same couplings by Magic Angle Spinning techniques.

<span class="mw-page-title-main">Chromium(I) hydride</span> Chemical compound

Chromium(I) hydride, systematically named chromium hydride, is an inorganic compound with the chemical formula (CrH)
n
. It occurs naturally in some kinds of stars where it has been detected by its spectrum. However, molecular chromium(I) hydride with the formula CrH has been isolated in solid gas matrices. The molecular hydride is very reactive. As such the compound is not well characterised, although many of its properties have been calculated via computational chemistry.

<span class="mw-page-title-main">Iron(I) hydride</span> Chemical compound

Iron(I) hydride, systematically named iron hydride and poly(hydridoiron) is a solid inorganic compound with the chemical formula (FeH)
n
(also written ([FeH])
n
or FeH). It is both thermodynamically and kinetically unstable toward decomposition at ambient temperature, and as such, little is known about its bulk properties.

In spectroscopy, collision-induced absorption and emission refers to spectral features generated by inelastic collisions of molecules in a gas. Such inelastic collisions may induce quantum transitions in the molecules, or the molecules may form transient supramolecular complexes with spectral features different from the underlying molecules. Collision-induced absorption and emission is particularly important in dense gases, such as hydrogen and helium clouds found in astronomical systems.

<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.

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

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.

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.

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

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.

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

Dirubidium is a molecular substance containing two atoms of rubidium found in rubidium vapour. Dirubidium has two active valence electrons. It is studied both in theory and with experiment. The rubidium trimer has also been observed.

<span class="mw-page-title-main">Diargon</span> 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.

Borane(1), boron monohydride, hydridoboron or borylene is the molecule with the formula BH. It exists as a gas but rapidly degrades when condensed. By contrast, the cluster B12H122- (dodecaborate), which has very similar empirical formula, forms robust salts.

John Morrissey Doyle is an American physicist working in the field of Atomic, Molecular, and Optical (AMO) physics and Precision Particle Physics. He is the Henry B. Silsbee Professor of Physics, Director of the Japanese Undergraduate Research Exchange Program (JUREP), Co-Director of the Harvard Quantum Initiative as well as Co-director of the Ph.D. Program in Quantum Science and Engineering at Harvard University.

References

  1. Barbuy, B.; Schiavon, R. P.; Gregorio-Hetem, J.; Singh, P. D.; Batalha, C. (October 1993). "Intensity of CaH Lines in Cool Dwarfs". Astronomy and Astrophysics Supplement Series. 101 (2): 409. Bibcode:1993A&AS..101..409B.
  2. Fowler, A. (1907). "The fluted spectrum of titanium oxide". Proceedings of the Royal Society A. 79 (533): 509–18. Bibcode:1907RSPSA..79..509F. doi: 10.1098/rspa.1907.0059 .
  3. 1 2 3 4 Frum, C.I.; H.M. Pickett (1993). "High-Resolution Infrared Fourier Transform Emission Spectroscopy of Metal Hydrides: X2Σ+ state of CaH". Journal of Molecular Spectroscopy. 159 (2): 329–336. Bibcode:1993JMoSp.159..329F. doi:10.1006/jmsp.1993.1130.
  4. Olmsted, Charles M. (1908). "Sun-spot bands which appear in the spectrum of a calcium arc burning in the presence of hydrogen". Contributions from the Solar Observatory of the Carnegie Institution of Washington. 21: 1–4. Bibcode:1908CMWCI..21....1O.
  5. Hulthèn, E. (1 January 1927). "On The Band Spectrum of Calcium Hydride". Physical Review. 29 (1): 97–111. Bibcode:1927PhRv...29...97H. doi:10.1103/PhysRev.29.97.
  6. Watson, William; Weber, Robert (1 November 1935). "The E Band System of Calcium Hydride". Physical Review. 48 (9): 732–734. Bibcode:1935PhRv...48..732W. doi:10.1103/PhysRev.48.732.
  7. Öhman, Yngve (October 1934). "Spectrographic Studies in the Red". Astrophysical Journal. 80: 171. Bibcode:1934ApJ....80..171O. doi:10.1086/143595.
  8. Bretislav Friedrich; John M. Doyle (2009). "Why are Cold Molecules so Hot?". ChemPhysChem. 10 (4): 604–623. doi:10.1002/cphc.200800577. PMID   19229896.
  9. 1 2 Doyle, John M.; Jonathan D. Weinstein; Robert deCarvalho; Thierry Guillet; Bretislav Friedrich (1998). "Magnetic trapping of calcium monohydride molecules at millikelvin temperatures". Nature. 395 (6698): 148–150. Bibcode:1998Natur.395..148W. doi:10.1038/25949. S2CID   38268509.
  10. 1 2 3 4 5 Holka, Filip; Miroslav Urban (2006). "The dipole moment and molecular properties of CaH: A theoretical study". Chemical Physics Letters. 426 (4–6): 252–256. Bibcode:2006CPL...426..252H. doi:10.1016/j.cplett.2006.05.108.
  11. Steimle, T. C.; Jinhai Chen; Jamie Gengler (2004-07-08). "The permanent electric dipole moments of calcium monohydride, CaH". The Journal of Chemical Physics. 121 (2): 829–834. Bibcode:2004JChPh.121..829S. doi:10.1063/1.1759314. PMID   15260612.
  12. Ram, R.S.; Tereszchuk, K.; Gordon, I.E.; Walker, K.A.; Bernath, P.F. (2011). "Fourier transform emission spectroscopy of the E2Π–X2Σ+ transition of CaH and CaD". Journal of Molecular Spectroscopy. 266 (2): 86–91. Bibcode:2011JMoSp.266...86R. doi:10.1016/j.jms.2011.03.009.
  13. Gordon, I.; Ram, R. S.; Tereszchuk, K.; Walker, K. A.; Bernath, P. F. (1 April 2011). "Fourier Transform Emission Spectroscopy of the E2Π–X2Σ+ System of CaH and CaD". Ohio State University. hdl: 1811/49445 .
  14. Berg, L-E; L Klynning (1974). "Rotational Analysis of the A-X and B-X Band Systems of CaH". Physica Scripta. 10 (6): 331–336. Bibcode:1974PhyS...10..331B. doi:10.1088/0031-8949/10/6/009. S2CID   250910373.
  15. 1 2 3 4 Pereira, R.; S. Skowronek; A. González Ureña; A. Pardo; J.M.L. Poyato; A.H. Pardo (2002). "Rotationally Resolved REMPI Spectra of CaH in a Molecular Beam". Journal of Molecular Spectroscopy. 212 (1): 17–21. Bibcode:2002JMoSp.212...17P. doi:10.1006/jmsp.2002.8531.
  16. Barclay, W. L. Jr.; Anderson, M. A.; Ziurys, L. M. (1993). "The millimeter-wave spectrum of CaH (X 2Σ+)". Astrophysical Journal Letters. 408 (1): L65–L67. Bibcode:1993ApJ...408L..65B. doi: 10.1086/186832 .
  17. Singh, Vijay; Kyle S. Hardman; Naima Tariq; Mei-Ju Lu; Aja Ellis; Muir J. Morrison; Jonathan D. Weinstein (2012). "Chemical Reactions of Atomic Lithium and Molecular Calcium Monohydride at 1 K". Physical Review Letters. 108 (20): 203201. Bibcode:2012PhRvL.108t3201S. doi: 10.1103/PhysRevLett.108.203201 . hdl: 20.500.11937/20342 . PMID   23003146.