Quantum Theory

Planck’s radiation law

By the end of the 19th century, physicists almost universally accepted the wave theory of light. However, though the ideas of classical physics explain interference and diffraction phenomena relating to the propagation of light, they do not account for the absorption and emission of light. All bodies radiate electromagnetic energy as heat; in fact, a body emits radiation at all wavelengths. The energy radiated at different wavelengths is a maximum at a wavelength that depends on the temperature of the body; the hotter the body, the shorter the wavelength for maximum radiation. Attempts to calculate the energy distribution for the radiation from a blackbody using classical ideas were unsuccessful. (A blackbody is a hypothetical ideal body or surface that absorbs and reemits all radiant energy falling on it.) One formula, proposed by Wilhelm Wien of Germany, did not agree with observations at long wavelengths, and another, proposed by Lord Rayleigh (John William Strutt) of England, disagreed with those at short wavelengths.

In 1900 the German theoretical physicist Max Planck made a bold suggestion. He assumed that the radiation energy is emitted, not continuously, but rather in discrete packets called quanta. The energy E of the quantum is related to the frequency ν by E = hν. The quantity h, now known as Planck’s constant, is a universal constant with the approximate value of 6.62607 × 10−34 joule∙second. Planck showed that the calculated energy spectrum then agreed with observation over the entire wavelength range.

Einstein and the photoelectric effect

In 1905 Einstein extended Planck’s hypothesis to explain thephotoelectric effect, which is the emission of electrons by a metal surface when it is irradiated by light or more-energetic photons. The kinetic energy of the emitted electrons depends on the frequency ν of the radiation, not on its intensity; for a given metal, there is a threshold frequency ν0 below which no electrons are emitted. Furthermore, emission takes place as soon as the light shines on the surface; there is no detectable delay. Einstein showed that these results can be explained by two assumptions: (1) that light is composed of corpuscles or photons, the energy of which is given by Planck’s relationship, and (2) that an atom in the metal can absorb either a whole photon or nothing. Part of the energy of the absorbed photon frees an electron, which requires a fixed energy W, known as the work function of the metal; the rest is converted into the kinetic energy meu2/2 of the emitted electron (me is the mass of the electron and u is its velocity). Thus, the energy relation is 

If ν is less than ν0, where hν0 = W, no electrons are emitted. Not all the experimental results mentioned above were known in 1905, but all Einstein’s predictions have been verified since.

Bohr’s theory of the atom

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A major contribution to the subject was made by Niels Bohr of Denmark, who applied the quantum hypothesis to atomic spectra in 1913. The spectra of light emitted by gaseous atoms had been studied extensively since the mid-19th century. It was found that radiation from gaseous atoms at low pressure consists of a set of discrete wavelengths. This is quite unlike the radiation from a solid, which is distributed over a continuous range of wavelengths. The set of discrete wavelengths from gaseous atoms is known as a line spectrum, because the radiation (light) emitted consists of a series of sharp lines. The wavelengths of the lines are characteristic of the element and may form extremely complex patterns. The simplest spectra are those of atomic hydrogen and the alkali atoms (e.g., lithium, sodium, and potassium). For hydrogen, the wavelengths λ are given by the empirical formula 

where m and n are positive integers with n > m and R∞, known as theRydberg constant, has the value 1.097373157 × 107 per metre. For a given value of m, the lines for varying n form a series. The lines for m = 1, the Lyman series, lie in the ultraviolet part of the spectrum; those for m = 2, the Balmer series, lie in the visible spectrum; and those for m = 3, the Paschen series, lie in the infrared.

Bohr started with a model suggested by the New Zealand-born British physicist Ernest Rutherford. The model was based on the experiments ofHans Geiger and Ernest Marsden, who in 1909 bombarded gold atoms with massive, fast-moving alpha particles; when some of these particles were deflected backward, Rutherford concluded that the atom has a massive, charged nucleus. In Rutherford’s model, the atom resembles a miniature solar system with the nucleus acting as the Sun and the electrons as the circulating planets. Bohr made three assumptions. First, he postulated that, in contrast to classical mechanics, where an infinite number of orbits is possible, an electron can be in only one of a discrete set of orbits, which he termed stationary states. Second, he postulated that the only orbits allowed are those for which the angular momentum of the electron is a whole number n times ℏ (ℏ = h/2π). Third, Bohr assumed that Newton’s laws of motion, so successful in calculating the paths of the planets around the Sun, also applied to electrons orbiting the nucleus. The force on the electron (the analogue of the gravitational force between the Sun and a planet) is the electrostatic attraction between the positively charged nucleus and the negatively charged electron. With these simple assumptions, he showed that the energy of the orbit has the form

where E0 is a constant that may be expressed by a combination of the known constants e, me, and ℏ. While in a stationary state, the atom does not give off energy as light; however, when an electron makes a transition from a state with energy En to one with lower energy Em, a quantum of energy is radiated with frequency ν, given by the equation

 Inserting the expression for En into this equation and using the relation λν = c, where c is the speed of light, Bohr derived the formula for the wavelengths of the lines in the hydrogen spectrum, with the correct value of the Rydberg constant.

Bohr’s theory was a brilliant step forward. Its two most important features have survived in present-day quantum mechanics. They are (1) the existence of stationary, nonradiating states and (2) the relationship of radiation frequency to the energy difference between the initial and final states in atransition. Prior to Bohr, physicists had thought that the radiation frequency would be the same as the electron’s frequency of rotation in an orbit.