1 Hydrogen

There are three isotopes of hydrogen: protium, deuterium, and tritium. Some of the fundamental properties of these isotopes, including nuclear, atomic, and molecular ones, are listed in Table 1.1 [1.11.5] for convenience of later reference. The elemental hydrogen exists in several dierent forms; as a monatomic gas at low densities, diatomic molecules under ordinary conditions, a metallic conductor at high pressures, and as an ionized plasma at very high temperatures. All these states are realized in dierent places in the Solar System, but on Earth, the elemental hydrogen usually exists only as molecules. In this chapter, we deal exclusively with the molecular form of elemental hydrogen.

1.1 Molecules
Molecular hydrogen is a very stable entity. Its electronic ground state, the singlet state 1 0 has an energy lower than two atoms by E0 = 4.748 eV g (the binding energy), and the equilibrium separation is very short, being A r0 = 0.7416 . The electronic energy as a function of internuclear separation r (the adiabatic potential) and energy levels of the stretching vibration are shown in Fig. 1.1 [1.6]. 0 For an H2 molecule, the zero-point vibration energy is Ev = 0.372 eV, and accordingly, the dissociation energy is
0 Ed = E0 Ev = 4.476 eV .

(1.1)

The dissociation energy becomes isotope-dependent due to the isotope de0 pendence of Ev . The energy of rotation along the two axes perpendicular to the molecular axis is smaller in comparison. Due to large excitation energies of the stretching vibration, most of the molecules are in the ground state (nv = 0) at ordinary temperatures (T 2000 K), and its partition function can be approximately written as

Zv =
nv =0

eEv

nv

/kT

0 eEv /kT =

(1.2)

The partition function for the rotational motion

1 Hydrogen Table 1.1. Some properties of hydrogen isotopes H D 1.998 1 0.8574 T 2.993 1/2 2.9788

Nucleus Nuclear mass [Mp ] Nuclear spin Nuclear moment [B ] Atom (1s1 ) Ionization energy [eV] Molecule (1 + )) g Binding energy E0 [eV] Dissociation energy Ed [eV] 0 Vibrational energya Ev [eV] Rotational energya Br [eV] Gasliquid (normal) Critical point Temperature [K] Pressure [MPa] Boiling point at 0.1 MPa Temperature [K] Latent heat [J mol1 ] Gasliquidsolid (normal) Triple point Temperature [K] Pressure [kPa]
a

1.000 1/2 2.7928

13.5989

13.6025

13.6038

4.748 4.478 0.5160 7.32 103

4.748 4.556 0.3712 3.70 103

4.59 0.3402

32.98 1.298 20.41 913

38.34 1.649 23.67 1235

40.44 1.906 25.04 1394

13.96 7.20

18.73 17.15

20.62 21.60

Calculated from lowest excitation energies.

Jr =0

Zr =

1 2

(2Jr + 1)eEr /kT

J

(1.3) (1.4)

J Er = Br Jr (Jr + 1)

Jr = 0, 1, 2, . . .

can be approximately given by kT 4 2 Ir kT Zr = = 2Br h2 (1.5)

2 where Ir = 1 /2 M r0 is the moment of inertia of the molecule. One important issue regarding the rotational motion is the existence of two distinct states, ortho(o)- and para(p)-states. The distinction comes from the requirement that the wave function of a molecule must be antisymmeteric

1.1 Molecules

Fig. 1.1. Adiabatic potential and energy levels of the stretching vibration of H2 molecule [1.6]

with respect to the interchange of the space coordinates of the two constituent fermions, and symmetric for interchange of bosons. Since the wave functions of the electronic ground state and vibrational states are symmetric with the interchange of the two nuclei, the symmetry requirement must be satised by the product of rotational and nuclear wave functions. In the case of protons and tritons (fermions) with nuclear spin I = 1/2, antisymmetric (odd Jr ) and symmetric (even Jr ) rotational states must be coupled with symmetric and antisymmetric nuclear states,respectively. These two groups of molecules are called o-H2 (o-T2 ) and p-H2 (p-T2 ), respectively. In the case of deuterons (bosons) with nuclear spin I = 1, on the other hand, they must be coupled with antisymmetric and symmetric rotational states, respectively. The energies and wave functions of rotational states of an H2 molecule are shown in Fig. 1.2. Note, in particular, that hydrogen molecules do not always look like dumbbells; molecules in the Jr = 0 rotational state, the ground state of p-H2 (p-T2 ) and o-D2 , are spherically symmetric. As there are (2I + 1)(I + 1) symmetric and (2I + 1)I antisymmetric states for nuclear spin I, the population ratio of o-H2 (o-T2 ) and p-H2 (p-T2 ) in thermal equilibrium is give by No = Np (I + 1) I
Jr =odd J qr Jr =even
J

J qr

(1.6) (1.7)

J qr = (2Jr + 1)eEr /kT .

1 Hydrogen

Fig. 1.2. Energy and wave functions of rotational states of para-H2 and ortho-H2 molecule. I, the total nuclear spin, is 0 or 1, Jr , the rotational quantum number is 0, 1, 2, . . . [1.2]

As a function of temperature this ratio starts from zero at T = 0, and increases monotonically to (I + 1)/I at high temperatures (already 2.990 at 300 K). In the case of D2 , the corresponding expression becomes
J I qr Np Jr =odd = , J No (I + 1) qr Jr =even

(1.8)

and approaches 0.5 at high temperatures (0.4999 at 200 K). Thus, at room temperature and above, H2 (T2 ) gas can be regarded as a 3:1 mixture of o-H2 (o-T2 ) and p-H2 (p-T2 ), and D2 gas as a 2:1 mixture of o-D2 and p-D2 . These mixtures are called normal hydrogens (n-H2 , D2 , or T2 ). Under ordinary circumstances, conversion between ortho and para states is so slow that the orthopara ratio can be regarded to be constant during cooling to low temperatures. This slow orthopara conversion acts as an internal heat source that causes evaporation of hydrogen at low temperatures. In order to attain the thermal-equilibrium population in the course of cooling, a gas mixture must be placed in contact with some catalyst, such as charcoal or nickel-silica. In view of the apparent simplicity of the hydrogen molecule, it may come as a surprise to learn that the complete assignment of the energy-level structure was achieved rather recently in 1970s. Since then, however, molecular

1.2 Description as an Ideal Gas

hydrogen has been the prototype for the investigation of the electronnuclear coupling, namely, how electronic energy is converted to the nucleis vibrational and rotational energy, and vice versa. The study of these intramolecular interactions provides a physical basis for the chemical reactions involving hydrogen. The recent advances of the molecular physics of hydrogen were described by Dehmer [1.7].

1.2 Description as an Ideal Gas

The molecular hydrogen exists in three dierent states, gas, liquid and solid, as shown in Fig. 1.3 [1.8]. The triple point is located at Tt = 13.96 K and pt = 7.20 kPa, and the gasliquid critical point at Tc = 32.98 K and pc = 1.298 MPa.

Fig. 1.3. pT phase diagram of hydrogen. Tt and Tc signify the triple point and the critical point, respectively [1.8]

Under ordinary conditions adopted for the investigation of MH alloys (T > 300 K, p < 10 MPa), hydrogen can be described reasonably well as an ideal gas. The chemical potential (per molecule) is given by g = kT ln p0 (T ) = p Ed p0 (T ) (1.9) (1.10)

(4M kT )3/2 kT 4 2 Ir kT . h5

Here, the energy has been measured from two dissociated H atoms. Then, the enthalpy and entropy of gaseous hydrogen per molecule can be obtained as

1 Hydrogen

7 kT Ed 2 p 7 . sg /k = ln 2 p0 (T ) hg =

(1.11) (1.12)

It is often convenient to isolate the pressure dependence of g and sg , and express these quantities by taking the gas of pressure p0 = 0.1 MPa (1 atom) as standard. Thus, g g0 = T (sg sg0 ) = kT ln p0 (T ) Ed p0 p0 (T ) 7 sg0 /k = + ln . 2 p0 g0 = kT ln For convenience, we may write p0 (T ) = p0 T T
7/2

p p0

(1.13) (1.14) (1.15)

T = 9.20 K .

(1.16)

It must be recognized that deviations from the ideal-gas behavior, though small, may not be totally negligible for some purposes. At 300 K and 10 MPa, the actual volume V is larger than the ideal-gas volume Vid by 6.0%, which leads to the increase of the chemical potential
p

=
0

(V Vid ) dp

(1.17)

by 1.1% over the ideal-gas value (see Table 4.1). Thermodynamical properties of molecular hydrogen under more extended p, T conditions are described in Chap. 4.

1.3 Some Characteristic Properties of Hydrogen

Hydrogen as an element has various unique features, including in particular its reactivity with many dierent elements, even at very low temperatures in some cases. The anomalous dependence of the reactivity and various other properties on temperature and isotope mass have been taken to be the evidence that some quantum tunneling processes are involved. In broad terms, these unique features can be ascribed to (a) a medium value of the electronegativity, (b) a small atomic size, and (c) a small nuclear mass. In the following, these points are discussed in slightly more detail to bring out some of the most characteristic features of the MH system.

1.3 Some Characteristic Properties of Hydrogen

(a) The Medium Electronegativity The electronegativity describes the degree of easiness of attaching an electron to and/or diculty of detaching an electron from a neutral atom, and serves as a useful measure for predicting the type of bonds to be formed between a pair of elements. Thus, if A < B holds for the electronegativity of elements A and B, one electron will be transferred from A to B to form A+ B . If, instead, A B , a chemical bond without a charge transfer, either a covalent bond or a metallic bond, is likely to form. The fact that hydrogen has a medium value of the electronegativity [1.9] indicates that it may form various kinds of chemical bonds with various elements. An implication of this fact to the MH system is discussed in the introduction to Chap. 2. (b) The Small Size One might consider intuitively that a hydrogen atom should be small in size because it has only a small number of electrons around. The situation is in fact not so simple. Of the three charged states of hydrogen, an H ion has an ionic radius of 2.1 , which is large and comparable to heavy halogens (1.95 A A A for Br and 2.16 for I ). The size of a neutral atom H0 as measured by A the Bohr radius is aB = 0.529 . For an H+ ion, the ionic radius of Shannon and Prewitt is (0.18 0.38) depending on the number of surrounding A anions [1.10,1.11]. Considering that an H+ ion is in fact a bare proton, it may appear strange to speak about its size, especially its negative value. What this actually implies is that the presence of a proton causes contraction of the neighboring bonds by the eect of hydrogen bonding. When a hydrogen atom is placed in a metallic environment, conduction electrons screen the proton charge at short distances to make it appear as a neutral atom. Electronic calculations performed for hydrogen in transition metals have shown that 1s-like orbitals around the proton are strongly hybridized with d-orbitals of surrounding M-atoms to form bonding states (see Chap. 7). Thus, the apparent small size of an H atom, that allows it to enter narrow interstitial sites in metal lattices, is due in part to the exibility of surrounding electronic states. A small positive charge on a proton leaves the surrounding electrons easily adaptable to given circumstances. (c) The Small Nuclear Mass In a molecular form, a small nuclear mass combined with strong binding forces makes the vibrational energy levels widely spaced and isotope dependent. Thus, the isotope dependence manifests itself in the heat of dissociation and many other thermodynamical properties, as shown in Table 1.1. In alloys comprising M- and H-atoms of large mass dierences, the frequency distribution of the coupled oscillator system comes to be separated into a low-frequency component (acoustic-mode vibrations) very similar to

1 Hydrogen

the lattice vibration of the host metal, and a high-frequency component (optic-mode vibration) of interstitial H atoms. In comparison to typical vibration energies of M-lattices, the vibration energies of interstitial H atoms are usually much higher, being 50 200 meV (see Chap. 5). These values are an order of magnitude smaller than in a molecule but, being comparable to thermal energies at ordinary temperatures, aect the stability of phases and/or the preference of the type of interstitial sites. Another important aspect of the H vibration is the nite extension of its wave functions. In the adiabatic approximation, where an H atom is viewed as executing a vibrational motion in the potential eld of slowly moving M atoms, the H atom may be described, approximately, by wave functions of harmonic oscillators. The ground-state wave function has a spatial variation 2 of e(x/x0 ) , where x0 is given by h/ 2M E . Substituting the proton mass A and the excitation energy E = 0.1 eV, we obtain x0 = 0.29 . This value is A comparable to the spatial extension of the H-1s orbital aB = 0.529 , and by convolution, leads to an eective size of 0.8 . A These estimates of the spatial extension of the wave function immediately point to the possibility of tunneling of an H atom between interstitial sites. In bcc metals, in which the spacing between neighboring tetrahedral sites is 1.0 , evidence of tunneling processes was indeed observed. The tunneling A of H atoms is believed to become much more important on the surface of metals where the undulation of potentials is believed to be much smaller. The occurrence of tunneling processes is one of the most important consequences of the light mass of H. A quantum-mechanical description of interstitial H atoms in metals is one of the central issues of this book, and elucidated in Chaps. 56.