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.
Formation The neutral molecule can be formed in a low pressure gas discharge tube. A neutral beam of H3 can be formed from a beam of H+3 ions passing through gaseous potassium, which donates an electron to the ion, forming K+. Other gaseous alkali metals, such as caesium, can also be used to donate electrons. H+3 ions can be made in a duoplasmatron where an electric discharge passed through low pressure molecular hydrogen. This causes some H2 to become H+2. Then H2 + H+2 → H+3 + H. The reaction is exothermic with an energy of 1.7 eV, so the ions produced are hot with much vibrational energy. These can cool down via collisions with cooler gas if the pressure is high enough. This is significant because strongly vibrating ions produce strongly vibrating neutral molecules when neutralised according to the Franck–Condon principle.
Breakup H3 can break up in the following ways:
H3 → H+3 + e− H3 → H + H2 H3 → 3 H 2 H3 → 3 H2
Properties The molecule can only exist in an excited state. The different excited electronic states are represented by symbols for the outer electron nLΓ with n the principal quantum number, L is the electronic angular momentum, and Γ is the electronic symmetry selected from the D3h group. Extra bracketed symbols can be attached showing vibration in the core: {s,dl} with s representing symmetrical stretch, d degenerate mode, and l vibrational angular momentum. Yet another term can be inserted to indicate molecular rotation: (N,G) with N angular momentum apart from electrons as projected on the molecular axis, and G the Hougen's convenient quantum number determined by G=l+λ-K. This is often (1,0), as the rotational states are restricted by the constituent particles all being fermions. Examples of these states are: 2sA1' 3sA1' 2pA2" 3dE' 3DE" 3dA1' 3pE' 3pA2". The 2p2A2" state has a lifetime of 700 ns. If the molecule attempts to lose energy and go to the repulsive ground state, it spontaneously breaks up. The lowest energy metastable state, 2sA1' has an energy -3.777 eV below the H+3 and e− state but decays in around 1 ps. The unstable ground state designated 2p2E' spontaneously breaks up into a H2 molecule and an H atom. Rotationless states have a longer life time than rotating molecules. The electronic state for a trihydrogen cation with an electron delocalized around it is a Rydberg state. The outer electron can be boosted to high Rydberg state, and can ionise if the energy gets to 29562.6 cm−1 above the 2pA2" state, in which case H+3 forms.
Shape The shape of the molecule is predicted to be an equilateral triangle. Vibrations can occur in the molecule in two ways, firstly the molecule can expand and contract retaining the equilateral triangle shape (breathing), or one atom can move relative to the others distorting the triangle (bending). The bending vibration has a dipole moment and thus couples to infrared radiation.
Spectrum Gerhard Herzberg was the first to find spectroscopic lines of neutral H3 when he was 75 years old in 1979. Later he announced that this observation was one of his favourite discoveries. The lines came about from a cathode discharge tube. The reason that earlier observers could not see any H3 spectral lines, was due to them being swamped by the spectrum of the much more abundant H2. The important advance was to separate out H3 so it could be observed alone. Separation uses mass spectrometry separation of the positive ions, so that H3 with mass 3 can be separated from H2 with mass 2. However there is still some contamination from HD, which also has mass 3. The spectrum of H3 is mainly due to transitions to the longer lived state of 2p2A2". The spectrum can be measured via a two step photo-ionization method. Transitions dropping to the lower 2s2A1' state are affected by its very short lifetime in what is called predissociation. The spectral lines involved are broadened. In the spectrum there are bands due to rotation with P Q and R branches. The R branch is very weak in H3 isotopomer but strong with D3 (trideuterium).
The symmetric stretch vibration mode has a wave number of 3213.1 cm−1 for the 3s2A1' level and 3168 cm−1 for 3d2E" and 3254 cm−1 for 2p2A2". The bending vibrational frequencies are also quite similar to those for H+3.
Levels
Cation The related H+3 ion is the most prevalent molecular ion in interstellar space. It is believed to have played a crucial role in the cooling of early stars in the history of the Universe through its ability readily to absorb and emit photons. One of the most important chemical reactions in interstellar space is H+3 + e− → H3 and then → H2 + H.
Calculations Since the molecule is relatively simple, researchers have attempted to calculate the properties of the molecule ab-initio from quantum theory. The Hartree–Fock equations have been used.
Natural occurrence Triatomic hydrogen will be formed during the neutralization of H+3. This ion will be neutralised in the presence of gasses other than He or H2, as it can abstract an electron. Thus H3 is formed in the aurora in the ionosphere of Jupiter and Saturn.
History
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