“看见”一种新型的二维冰结构

 固体表面与水(冰)形成的界面是自然界中最常见的界面之一。它直接或者间接地影响到我们的日常生活以及工业技术的方方面面,对于该问题的科学研究涉及表面物理、大气化学、环境科学等多个领域。其中,水在固体表面发生的多相结晶过程是人们研究水和固体界面的一个重要方面。在地上,这种结冰过程能形成美丽的冰川,也会导致路面和铁轨结冰而阻碍交通;在空中,这种结冰过程是大气层循环中的一个重要组成部分,同时也是很多起飞机事故的元凶。     

Ab initio path-integral molecular dynamics and the quantum nature of hydrogen bonds

The hydrogen bond(HB) is an important type of intermolecular interaction, which is generally weak, ubiquitous,and essential to life on earth. The small mass of hydrogen means that many properties of HBs are quantum mechanical in nature. In recent years, because of the development of computer simulation methods and computational power, the influence of nuclear quantum effects(NQEs) on the structural and energetic properties of some hydrogen bonded systems has been intensively studied. Here, we present a review of these studies by focussing on the explanation of the principles underlying the simulation methods, i.e., the ab initio path-integral molecular dynamics. Its extension in combination with the thermodynamic integration method for the calculation of free energies will also be introduced. We use two examples to show how this influence of NQEs in realistic systems is simulated in practice.     

基于路径积分分子动力学与热力学积分方法的高压氢自由能计算

在相图研究中, 严格计算一个真实系统在特定温度、压强下的自由能是近年来该领域理论方法发展的前沿. 自Mermin提出有限温度密度泛函理论后, 在电子结构层面, 弱关联系统中人们就其在对自由能贡献的描述已相对完善, 但在原子核运动的描述上, 热运动与量子运动的非简谐项却总被忽视. 本文将路径积分分子动力学与热力学积分结合, 对300 GPa下氢晶体Cmca 结构中原子核热涨落与量子涨落对自由能的影响进行了分析. 发现在100 K核量子涨落非简谐项的贡献约为15 meV每原子, 远大于不同结构间静态焓的差别. 该研究提醒人们简谐近似在核量子效应描述中可能存在的不准确性(即使在低温下). 同时, 我们采取的方法 也为人们进行自由能的准确计算提供了一个简单有效的手段.     

Erratum to “ Accurate GW0 band gaps and their phonon-induced renormalization in solids”

The derivation of Eq. (28) in the original paper [Chin. Phys. B 30 117101 (2021)] is corrected.     

Concerted versus stepwise mechanisms of cyclic proton transfer: Experiments,simulations, and current challenges

Proton transfer (PT) is a process of fundamental importance in hydrogen (H)-bonded systems. At cryogenic or moderate temperatures, pronounced quantum tunneling may happen due to the light mass of H. Single PT processes have been extensively studied. However, for PT involving multiple protons, our understanding remains in its infancy stage due to the complicated interplay between the high-dimensional nature of the process and the quantum nature of tunneling. Cyclic H-bonded systems are typical examples of this, where PT can happen separately via a "stepwise" mechanism or collectively via a "concerted" mechanism. In the first scenario, some protons hop first, typically resulting in metastable intermediate states (ISs) and the reaction pathway passes through multiple transition states. Whilst in the concerted mechanism, all protons move simultaneously, resulting in only one barrier along the path. Here, we review previous experimental and theoretical studies probing quantum tunneling in several representative systems for cyclic PT, with more focus on recent theoretical findings with path-integral based methods. For gas-phase porphyrin and porphycene, as well as porphycene on a metal surface, theoretical predictions are consistent with experimental observations, and enhance our understanding of the processes. Yet, discrepancies in the PT kinetic isotope effects between experiment and theory appear in two systems, most noticeably in water tetramer adsorbed on NaCl (001) surface, and also hinted in porphycene adsorbed on Ag (110) surface. In ice I_h, controversy surrounding concerted PT remains even between experiments. Despite of the recent progress in both theoretical methods and experimental techniques, multiple PT processes in cyclic H-bonded systems remain to be mysterious.