Kammrath Aster, Griffin Graham B, Verlet Jan R R, Young Ryan M, Neumark Daniel M
Department of Chemistry, University of California, Berkeley, California 94720, USA.
J Chem Phys. 2007 Jun 28;126(24):244306. doi: 10.1063/1.2747618.
The dynamics of an excess electron in size-selected methanol clusters is studied via pump-probe spectroscopy with resolution of approximately 120 fs. Following excitation, the excess electron undergoes internal conversion back to the ground state with lifetimes of 260-175 fs in (CH3OH)n- (n=145-535) and 280-230 fs in (CD3OD)n- (n=210-390), decreasing with increasing cluster size. The clusters then undergo vibrational relaxation on the ground state on a time scale of 760+/-250 fs. The excited state lifetimes for (CH3OH)n- clusters extrapolate to a value of 157+/-25 fs in the limit of infinite cluster size.
通过分辨率约为120飞秒的泵浦-探测光谱研究了尺寸选择的甲醇团簇中多余电子的动力学。激发后，多余电子经历内转换回到基态，在(CH3OH)n-（n = 145 - 535）中的寿命为260 - 175飞秒，在(CD3OD)n-（n = 210 - 390）中的寿命为280 - 230飞秒，随团簇尺寸增加而减小。然后团簇在基态上以760±250飞秒的时间尺度经历振动弛豫。在无限团簇尺寸的极限下，(CH3OH)n-团簇的激发态寿命外推至157±25飞秒的值。
