Free-Energy Calculations in Soft and Hard Matter: From Early Challenges to the Advent of Umbrella Sampling

Daniele Macuglia – Department of History of Science, Technology and Medicine, Peking University

The elucidation of transformations across various states of matter depends critically on the accuracy of free-energy calculations. Tracing the evolution from the simulation techniques of the 1960s, through the emergence of free-energy calculations via molecular simulation, to the introduction of umbrella sampling in 1977, this talk examines the initial challenges and limitations encountered in early computational efforts, highlighting the innovative methodological developments spurred by those difficulties. Through a wide-ranging retrospective, I will shed light on the significant breakthroughs that have expanded the capabilities, increased the precision, and enhanced the reliability of molecular simulations in the study of condensed matter systems.