Grochala Wojciech, Hoffmann Roald, Feng Ji, Ashcroft Neil W
ICM and Department of Chemistry, Warsaw University, Warsaw 02-106, Poland.
Angew Chem Int Ed Engl. 2007;46(20):3620-42. doi: 10.1002/anie.200602485.
Diamond-anvil-cell and shock-wave technologies now permit the study of matter under multimegabar pressure (that is, of several hundred GPa). The properties of matter in this pressure regime differ drastically from those known at 1 atm (about 10(5) Pa). Just how different chemistry is at high pressure and what role chemical intuition for bonding and structure can have in understanding matter at high pressure will be explored in this account. We will discuss in detail an overlapping hierarchy of responses to increased density: a) squeezing out van der Waals space (for molecular crystals); b) increasing coordination; c) decreasing the length of covalent bonds and the size of anions; and d) in an extreme regime, moving electrons off atoms and generating new modes of correlation. Examples of the startling chemistry and physics that emerge under such extreme conditions will alternate in this account with qualitative chemical ideas about the bonding involved.
金刚石对顶砧细胞和冲击波技术现在允许在多兆巴压力（即几百吉帕斯卡）下研究物质。在这种压力状态下物质的性质与在1个大气压（约10⁵帕斯卡）下已知的性质截然不同。在本文中，我们将探讨高压下化学究竟有何不同，以及键合和结构的化学直觉在理解高压物质时能发挥什么作用。我们将详细讨论随着密度增加而产生的一系列重叠的响应：a）挤出范德华空间（对于分子晶体）；b）增加配位；c）缩短共价键长度和阴离子尺寸；d）在极端情况下，使电子离开原子并产生新的关联模式。在本文中，这种极端条件下出现的惊人化学和物理实例将与关于所涉及键合的定性化学观点交替出现。
