Soley Micheline B, Heller Eric J
Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, United States.
Department of Physics-Affiliate, University of Wisconsin-Madison, 1150 University Avenue, Madison, Wisconsin 53706, United States.
Chem Rev. 2025 Jul 23;125(14):6609-6652. doi: 10.1021/acs.chemrev.4c01014. Epub 2025 Jun 25.
Ultracold atoms and molecules provide an unprecedented view into the role of quantum effects in chemical reactions. However, these same quantum effects make ultracold chemical reactions notoriously difficult to simulate. Contrary to conventional wisdom that ultracold systems necessitate quantum approaches, with classical mechanics offering a rough approximation at best, the past three decades have seen an explosion in classical, quasiclassical, and semiclassical approaches that yield near-exact results for ultracold systems─including in cases where today's quantum methods would be computationally intractable. This review illustrates the power of these approaches with 30 years' worth of numerical and experimental evidence. The review provides a comprehensive account of the successes of universal classical post-threshold laws for low-energy atomic and molecular scattering systems, as well as the cutting edge in quasiclassical approaches that unravel the ongoing controversy surrounding long-lived collision complex lifetimes in ultracold collisions. Special attention is placed on atomic systems where classical scaling laws hold directly at zero Kelvin, which underline the predictive power classical methods can offer even in the most extreme quantum chemical environments. The review culminates with a discussion of broader implications for classically inspired approaches to prototypically quantum chemistry in the second quantum revolution.
超冷原子和分子为研究量子效应在化学反应中的作用提供了前所未有的视角。然而,正是这些相同的量子效应使得超冷化学反应极难模拟。与传统观念相反,传统观念认为超冷系统需要量子方法,而经典力学充其量只能提供粗略的近似,在过去三十年里,经典、准经典和半经典方法大量涌现,这些方法对于超冷系统能产生近乎精确的结果——包括在当今量子方法在计算上难以处理的情况下。这篇综述用三十年的数值和实验证据说明了这些方法的强大之处。该综述全面阐述了低能原子和分子散射系统通用经典阈后定律的成功之处,以及准经典方法的前沿进展,这些方法解开了围绕超冷碰撞中长寿命碰撞复合物寿命的持续争议。特别关注了在零开尔文时经典标度律直接适用的原子系统,这凸显了经典方法即使在最极端的量子化学环境中也能提供的预测能力。综述最后讨论了在第二次量子革命中,经典启发方法对典型量子化学的更广泛影响。