CAJ | 학술논문

利用时间分辨飞秒光电子影像技术结合时间分辨质谱技术,研究了氯苯分子第一激发态的超快过程.266,7 nm单光子将氯苯分子激发至第一激发态.母体离子时间变化曲线包括了不同的双指数曲线.一个是时间常数为(152±3)fs的快速组分,另一个是时间常数为(749±21)ps的慢速组分.通过时间分辨的光电子影像得到了时间分辨的光电子动能分布和角度分布.时间常数为(152±3)fs的快速组分反映了第一激发态内部的能量转移过程,这个过程归属为氯苯分子第一激发态耗散型振动驰豫过程.时间常数为(749±21)ps的慢速组分反映了第一激发态的慢速内转换过程.另外,实验实时观察到典型的非对称陀螺分子(氯苯)激发态的非绝热准直和转动退相干现象.并推算出第一次转动恢复时间为205.8 ps(C类型)和359.3 ps (J类型).
이용시간분변비초광전자영상기술결합시간분변질보기술,연구료록분분자제일격발태적초쾌과정.266,7 nm단광자장록분분자격발지제일격발태.모체리자시간변화곡선포괄료불동적쌍지수곡선.일개시시간상수위(152±3)fs적쾌속조분,령일개시시간상수위(749±21)ps적만속조분.통과시간분변적광전자영상득도료시간분변적광전자동능분포화각도분포.시간상수위(152±3)fs적쾌속조분반영료제일격발태내부적능량전이과정,저개과정귀속위록분분자제일격발태모산형진동치예과정.시간상수위(749±21)ps적만속조분반영료제일격발태적만속내전환과정.령외,실험실시관찰도전형적비대칭타라분자(록분)격발태적비절열준직화전동퇴상간현상.병추산출제일차전동회복시간위205.8 ps(C류형)화359.3 ps (J류형).
Ultrafast dynamics of the first excited state (S1) of chlorobenzene was studied using a combination of femtosecond time-resolved photoelectron imaging and time-resolved mass spectroscopy.One-photon absorption at 266.7 nm was used to populate the S1 state of chlorobenzene. The time evolution of the parent ion signals consists of different biexponential decays. One is a fast component on a timescale of (152±3) fs and the other is a slow component with a timescale of (749±21) ps. Timeresolved electron kinetic energies (eKE) and time-resolved photoelectron angular distributions (PADs)were extracted from time-resolved photoelectron imaging and are discussed in detail. The ultrafast process with a time constant of (152 ± 3) fs is a population transfer within the S1 state, and only a vibrational energy transfer process with strong coupling is a reasonable explanation. This is attributed to an ultrafast process of dissipative intramolecular vibrational energy redistribution (IVR). The lifetime of the S1 state was determined to be (749±21) ps, and its deactivation was due to slow internal conversion to the ground state. Additionally, nonadiabatic alignment and rotational dephasing of the S1 state of chlorobenzene, as a typical asymmetric top molecule, were observed. The first C-type and J-type recurrences are expected at delay time of 205.8 and 359.3 ps, respectively.