Quantum Low-Temperature Limit of a Chemical Reaction Rate

Science  28 Dec 1973:
Vol. 182, Issue 4119, pp. 1344-1345
DOI: 10.1126/science.182.4119.1344


The radiation-induced polymerization of formaldehyde has been studied in the solid state. The time of addition of one new link to a polymer chain increases exponentially in accordance with the Arrhenius law at 140 to 80 K, but approaches a constant value (approximately 10-2 second) at temperatures below 10 K. Thus, a low-temperature limit to a chemical reaction rate has been observed. It is interpreted as a quantum effect caused by tunneling from the zero vibration level of the initial state, and a semiquantitative theory is given. The phenomenon should be taken into account for understanding tunneling of electrons in biological systems when such tunneling is accompanied by conformational changes. It could also be significant in slow, exothermic chemical reactions at low and ultralow temperatures, which may have had a role in chemical and biological evolution (cold prehistory of life?).