With the advent of attosecond light pulses at the beginning of this century, the possibility to perform real‐time observations of electron motion in molecules has spurred impressive theoretical developments aimed at providing support and guidance to numerous, but still incipient, experimental efforts devoted to understand chemistry at its ultimate temporal frontier: the attosecond. The first real‐time observation of electron dynamics in a relatively large molecule, phenylalanine, was reported in 2014. This would have been difficult without the help of theory, since observations in this emerging field, recently coined attochemistry, are still indirect. While standard Quantum Chemistry methods can describe excited bound‐state dynamics, new approaches incorporating scattering theory formalisms are needed to understand the interaction with attosecond pulses. Indeed, due to their short wavelengths, lying in the XUV and X‐ray spectral regions, the interaction of such pulses with any molecule inevitably leads to ionization, which requires describing the molecular ionization continuum. Also, because of their short duration (i.e., large bandwidth), ionization is accompanied by the formation of a molecular electronic wave packet (i.e., a coherent superposition of electronic states), which evolves in time and dictates the fate of the molecule at the longer time scales where chemistry shows up. Although much has already been done up to date, current bottlenecks in the field are to account for electron correlations during the ionization process and for the coupled electron and nuclear dynamics that follows. Past and ongoing theoretical efforts are described here along with experimental work towards the solid establishment of attochemistry.

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阿秒分子科学的量子化学

随着本世纪初亚秒级光脉冲的到来，对分子中电子运动进行实时观察的可能性刺激了令人印象深刻的理论发展，旨在为众多但仍处于初期的实验工作提供支持和指导，以帮助人们理解化学在其最终的时间边界：阿秒。2014年，首次报道了相对大分子苯丙氨酸中电子动力学的首次实时观察。如果没有理论的帮助，这将是困难的，因为在这个新兴领域，近来原子化学的观察仍然是间接的。虽然标准的量子化学方法可以描述激发的束缚态动力学，需要新的方法结合散射理论形式主义来理解与阿秒脉冲的相互作用。实际上，由于它们位于XUV和X射线光谱区域的短波长，此类脉冲与任何分子的相互作用不可避免地导致电离，这需要描述分子电离连续体。同样，由于其持续时间短（即大带宽），电离伴随着分子电子波包的形成（即电子态的相干叠加），其随着时间的流逝而变化，并决定了分子在该位置处的命运。出现化学反应的时间跨度较长。尽管到目前为止已经做了很多工作，该领域中的当前瓶颈在于解决电离过程中的电子相关性以及随之而来的电子和核动力学耦合问题。这里描述了过去和正在进行的理论工作，以及为稳固建立原子化学所做的实验工作。