Relativistic quantum chemistry

Relativistic quantum chemistry combines relativistic mechanics with quantum chemistry to calculate elemental properties and structure, especially for the heavier elements of the periodic table. A prominent example is an explanation for the color of gold: due to relativistic effects, it is not silvery like most other metals.

The term relativistic effects was developed in light of the history of quantum mechanics. Initially, quantum mechanics was developed without considering the theory of relativity. Relativistic effects are those discrepancies between values calculated by models that consider relativity and those that do not. Relativistic effects are important for heavier elements with high atomic numbers, such as lanthanides and actinides.

Relativistic effects in chemistry can be considered to be perturbations, or small corrections, to the non-relativistic theory of chemistry, which is developed from the solutions of the Schrödinger equation. These corrections affect the electrons differently depending on the electron speed compared with the speed of light. Relativistic effects are more prominent in heavy elements because only in these elements do electrons attain sufficient speeds for the elements to have properties that differ from what non-relativistic chemistry predicts.

History

Beginning in 1935, Bertha Swirles described a relativistic treatment of a many-electron system, despite Paul Dirac's 1929 assertion that the only imperfections remaining in quantum mechanics "give rise to difficulties only when high-speed particles are involved and are therefore of no importance in the consideration of the atomic and molecular structure and ordinary chemical reactions in which it is, indeed, usually sufficiently accurate if one neglects relativity variation of mass and velocity and assumes only Coulomb forces between the various electrons and atomic nuclei".

Theoretical chemists by and large agreed with Dirac's sentiment until the 1970s, when relativistic effects were observed in heavy elements. The Schrödinger equation had been developed without considering relativity in Schrödinger's 1926 article. Relativistic corrections were made to the Schrödinger equation (see Klein–Gordon equation) to describe the fine structure of atomic spectra, but this development and others did not immediately trickle into the chemical community. Since atomic spectral lines were largely in the realm of physics and not in that of chemistry, most chemists were unfamiliar with relativistic quantum mechanics, and their attention was on lighter elements typical for the organic chemistry focus of the time.

Dirac's opinion on the role relativistic quantum mechanics would play for chemical systems has been largely dismissed for two main reasons. First, electrons in s and p atomic orbitals travel at a significant fraction of the speed of light. Second, relativistic effects give rise to indirect consequences that are especially evident for d and f atomic orbitals. One can extend this to a larger element with an atomic number Z by using the expression <math>v \approx \frac{Zc}{137}</math> for a 1s electron, where v is its radial velocity, i.e., its instantaneous speed tangent to the radius of the atom. For gold with Z = 79, v ≈ 0.58c, so the 1s electron will be moving at 58% of the speed of light. Substituting this in for v/c in the equation for the relativistic mass, one finds that mrel = 1.22me, and in turn putting this in for the Bohr radius above one finds that the radius shrinks by 22%.

If one substitutes the "relativistic mass" into the equation for the Bohr radius it can be written

<math display="block">a_\text{rel} = \frac{\hbar \sqrt{1 - (v_\text{e}/c)^2{m_\text{e} c \alpha}.</math>

It follows that

thumb|right| Ratio of relativistic and nonrelativistic Bohr radii, as a function of electron velocity

The ratio of the relativistic and nonrelativistic Bohr radii is simply <math> 1 / \gamma </math>, which as a function of the electron velocity is a circular arc. The relativistic radius reduces strongly as the electron velocity approaches <math>c</math>.

When the Bohr treatment is extended to hydrogenic atoms, the Bohr radius becomes

<math display="block">r = \frac{n^2}{Z} a_0 = \frac{n^2 \hbar^2 4 \pi \varepsilon_0}{m_\text{e}Ze^2},</math>

where <math>n</math> is the principal quantum number, and Z is an integer for the atomic number. In the Bohr model, the angular momentum is given as <math>mv_\text{e}r = n\hbar</math>. Substituting into the equation above and solving for <math>v_\text{e}</math> gives

<math display="block">\begin{align}

r &= \frac{n^2 a_0}{Z} = \frac{n \hbar}{m v_\text{e, \\

v_\text{e} &= \frac{Z}{n^2 a_0} \frac{n \hbar}{m}, \\

\frac{v_\text{e{c} &= \frac{Z \alpha}{n} = \frac{Z e^2}{4 \pi \varepsilon_0 \hbar c n}.

\end{align}</math>

Substituting the second-last equality into the expression for the Bohr ratio mentioned above gives

<math>\frac{a_\text{rel{a_0} = \sqrt{1 - (Z \alpha / n)^2}</math>       and since <math> \alpha \approx 1 / 137,</math>

<math>\frac{a_\text{rel{a_0} \approx \sqrt{1 - \left(\frac {Z}{137 n}\right)^2}</math>

At this point one can see that a low value of <math>n</math> and a high value of <math>Z</math> results in <math>\frac{a_\text{rel{a_0} < 1</math>. This fits with intuition: electrons with lower principal quantum numbers will have a higher probability density of being nearer to the nucleus. A nucleus with a large charge will cause an electron to have a high velocity. A higher electron velocity means an increased electron relativistic mass, and as a result the electrons will be near the nucleus more of the time and thereby contract the radius for small principal quantum numbers.

Periodic table deviations

Mercury

Mercury (Hg) is a liquid down to approximately −39 °C, its melting point. Bonding forces are weaker for Hg–Hg bonds than for their immediate neighbors such as cadmium (m.p. 321 °C) and gold (m.p. 1064 °C). The lanthanide contraction only partially accounts for this anomaly.

Mercury gas is mostly monatomic, Hg(g). Hg2(g) rarely forms and has a low dissociation energy, as expected due to the lack of strong bonds.

Au2(g) and Hg(g) are analogous with H2(g) and He(g) with regard to having the same nature of difference. The relativistic contraction of the 6s2 orbital leads to gaseous mercury sometimes being referred to as a pseudo noble gas.

Caesium, the heaviest of the alkali metals that can be collected in quantities sufficient for viewing, has a golden hue, whereas the other alkali metals are silver-white. However, relativistic effects are not very significant at Z = 55 for caesium (not far from Z = 47 for silver). The golden color of caesium comes from the decreasing frequency of light required to excite electrons of the alkali metals as the group is descended. For lithium through rubidium, this frequency is in the ultraviolet, but for caesium it reaches the blue-violet end of the visible spectrum; in other words, the plasmonic frequency of the alkali metals becomes lower from lithium to caesium. Thus caesium transmits and partially absorbs violet light preferentially, while other colors (having lower frequency) are reflected; hence it appears yellowish.

Lead–acid battery

Without relativity, lead (Z = 82) would be expected to behave much like tin (Z = 50), so tin–acid batteries should work just as well as the lead–acid batteries commonly used in cars. However, calculations show that about 10 V of the 12 V produced by a 6-cell lead–acid battery arises purely from relativistic effects, explaining why tin–acid batteries do not work.

Inert-pair effect

In Tl(I) (thallium), Pb(II) (lead), and Bi(III) (bismuth) complexes a 6s2 electron pair exists. The inert pair effect is the tendency of this pair of electrons to resist oxidation due to a relativistic contraction of the 6s orbital. Wan et al. (2021) instead calculated a repulsive effect.

The stability of gold and platinum anions in compounds such as caesium auride.
The slightly reduced reactivity of francium compared with caesium.
About 10% of the lanthanide contraction is attributed to the relativistic mass of high-velocity electrons and the smaller Bohr radius that results.

Relativistic quantum chemistry

History

Periodic table deviations

Mercury

Lead–acid battery

Inert-pair effect

See also

References

Further reading