structural:scholar_edition
Discovery of free electrons outside matter

While studying electrical conductivity in rarefied gases in 1859, the German physicist Julius Plücker observed the radiation emitted from the cathode caused phosphorescent light to appear on the tube wall near the cathode; and the region of the phosphorescent light could be moved by application of a magnetic field. In 1869, Plücker's student Johann Wilhelm Hittorf found that a solid body placed in between the cathode and the phosphorescence would cast a shadow upon the phosphorescent region of the tube. Hittorf inferred that there are straight rays emitted from the cathode and that the phosphorescence was caused by the rays striking the tube walls. In 1876, the German physicist Eugen Goldstein showed that the rays were emitted perpendicular to the cathode surface, which distinguished between the rays that were emitted from the cathode and the incandescent light. Goldstein dubbed the rays cathode rays. Decades of experimental and theoretical research involving cathode rays were important in J. J. Thomson 's eventual discovery of electrons.

During the 1870s, the English chemist and physicist Sir William Crookes developed the first cathode-ray tube to have a high vacuum inside. He then showed in 1874 that the cathode rays can turn a small paddle wheel when placed in their path. Therefore, he concluded that the rays carried momentum. Furthermore, by applying a magnetic field, he was able to deflect the rays, thereby demonstrating that the beam behaved as though it were negatively charged. In 1879, he proposed that these properties could be explained by regarding cathode rays as composed of negatively charged gaseous molecules in a fourth state of matter in which the mean free path of the particles is so long that collisions may be ignored.

The German-born British physicist Arthur Schuster expanded upon Crookes's experiments by placing metal plates parallel to the cathode rays and applying an electric potential between the plates. The field deflected the rays toward the positively charged plate, providing further evidence that the rays carried negative charge. By measuring the amount of deflection for a given electric and magnetic field, in 1890 Schuster was able to estimate the charge-to-mass ratio of the ray components. However, this produced a value that was more than a thousand times greater than what was expected, so little credence was given to his calculations at the time. This is because it was assumed that the charge carriers were much heavier hydrogen or nitrogen atoms. Schuster's estimates would subsequently turn out to be largely correct.

In 1892 Hendrik Lorentz suggested that the mass of these particles (electrons) could be a consequence of their electric charge.

While studying naturally fluorescing minerals in 1896, the French physicist Henri Becquerel discovered that they emitted radiation without any exposure to an external energy source. These radioactive materials became the subject of much interest by scientists, including the New Zealand physicist Ernest Rutherford who discovered they emitted particles. He designated these particles alpha and beta, on the basis of their ability to penetrate matter. In 1900, Becquerel showed that the beta rays emitted by radium could be deflected by an electric field, and that their mass-to-charge ratio was the same as for cathode rays. This evidence strengthened the view that electrons existed as components of atoms.

In 1897, the British physicist J. J. Thomson, with his colleagues John S. Townsend and H. A. Wilson, performed experiments indicating that cathode rays really were unique particles, rather than waves, atoms or molecules as was believed earlier. By 1899 he showed that their charge-to-mass ratio, e / m, was independent of cathode material. He further showed that the negatively charged particles produced by radioactive materials, by heated materials and by illuminated materials were universal. Thomson measured m / e for cathode ray "corpuscles", and made good estimates of the charge e, leading to value for the mass m, finding a value 1400 times less massive than the least massive ion known: hydrogen. In the same year Emil Wiechert and Walter Kaufmann also calculated the e / m ratio but did not take the step of interpreting their results as showing a new particle, while J. J. Thomson would subsequently in 1899 give estimates for the electron charge and mass as well: e ~ 6.8 × 10 esu and m ~ 3 × 10 g

The name "electron" was adopted for these particles by the scientific community, mainly due to the advocation by G. F. FitzGerald, J. Larmor, and H. A. Lorentz. The term was originally coined by George Johnstone Stoney in 1891 as a tentative name for the basic unit of electrical charge (which had then yet to be discovered).

The electron's charge was more carefully measured by the American physicists Robert Millikan and Harvey Fletcher in their oil-drop experiment of 1909, the results of which were published in 1911. This experiment used an electric field to prevent a charged droplet of oil from falling as a result of gravity. This device could measure the electric charge from as few as 1–150 ions with an error margin of less than 0.3%. Comparable experiments had been done earlier by Thomson's team, using clouds of charged water droplets generated by electrolysis, and in 1911 by Abram Ioffe, who independently obtained the same result as Millikan using charged microparticles of metals, then published his results in 1913. However, oil drops were more stable than water drops because of their slower evaporation rate, and thus more suited to precise experimentation over longer periods of time.

Around the beginning of the twentieth century, it was found that under certain conditions a fast-moving charged particle caused a condensation of supersaturated water vapor along its path. In 1911, Charles Wilson used this principle to devise his cloud chamber so he could photograph the tracks of charged particles, such as fast-moving electrons.