Verlet Jan R R, Bragg Arthur E, Kammrath Aster, Cheshnovsky Ori, Neumark Daniel M
Department of Chemistry, University of California, Berkeley, California 94720, USA.
J Chem Phys. 2004 Nov 22;121(20):10015-25. doi: 10.1063/1.1809573.
Electron-nuclear relaxation dynamics are studied in Hg(n) (-) (11 <or= n <or= 16,n = 18) using time-resolved photoelectron imaging. The excess electron in the anion uniquely occupies the p band and is excited intraband by 1.53 eV pump photons; the subsequent dynamics are monitored by photodetachment at 3.06 eV and measurement of the photoelectron images as a function of pump-probe delay. The initially excited state decays on a time scale of approximately 10 ps, and subsequent relaxation dynamics reveal a smooth evolution of the photoelectron spectra towards lower electron kinetic energy over 50-100 ps. Qualitatively, the relaxation process is captured by a simple kinetic model assuming a series of radiationless transitions within a dense manifold of electronic states. All the clusters studied show similar dynamics with the exception of Hg(11) (-) in which the initially prepared state does not decay as quickly as the others.
利用时间分辨光电子成像技术研究了Hg(n) (-)（11≤n≤16，n = 18）中的电子-核弛豫动力学。阴离子中的多余电子独特地占据p带，并被1.53 eV的泵浦光子带内激发；随后的动力学过程通过3.06 eV的光剥离以及作为泵浦-探测延迟函数的光电子图像测量来监测。初始激发态在大约10 ps的时间尺度上衰减，随后的弛豫动力学揭示了光电子能谱在50 - 100 ps内朝着更低电子动能的平滑演化。定性地说，弛豫过程可以通过一个简单的动力学模型来描述，该模型假设在密集的电子态流形内发生一系列无辐射跃迁。除了Hg(11) (-)之外，所有研究的团簇都表现出相似的动力学，在Hg(11) (-)中，初始制备的状态不像其他团簇那样迅速衰减。
