Free-energy calculations in condensed matter: from early challenges to the advent of umbrella sampling

Abstract

The investigation of condensed matter transformations hinges on the precision of free-energy calculations. This article charts the evolution of molecular simulations, tracing their development from the techniques of the early 1960s, through the emergence of free-energy calculations toward the end of the decade, and leading to the advent of umbrella sampling in 1977. The discussion explores the inherent challenges and limitations of early simulational endeavors, such as the struggle with accurate phase-space sampling and the need for innovative solutions like importance sampling and multistage sampling methods. Taken together, the initial hurdles and subsequent adoption of advanced techniques exemplify the leap from analytical methods to effective computational strategies that enabled more reliable simulations. Further analysis of this narrative reveals the methodological breakthroughs as well as the setbacks that transformed the theoretical and practical understanding of condensed matter phenomena. A follow-up study will examine the shifts in free-energy calculations from the late 1970s into the 1980s.