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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Theoretical investigations of the time-resolved photodissociation dynamics of IBr~-
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Theoretical investigations of the time-resolved photodissociation dynamics of IBr~-

机译：IBr〜-时间分辨光解离动力学的理论研究

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The role of laser pulse width as well as other quantum mechanical effects in the interpretation of the observed time-resolved photoelectron spectra (TRPES) of IBr~- are investigated using conditions that are chosen to reproduce those used for the experimental study of Mabbs et al. [J. Chem. Phys. 2005, 122, 174305 ]. In that study, it was shown that one could correlate shifts in the frequency of the maximum in signal as a function of time to differences between the potential energies of the electronic states that are accessed by the pump and probe lasers. While this classical picture is attractive, it is based on a single trajectory with an initial I-Br separation that is ～0.3 ? longer than the equilibrium value. In addition, it does not include the role of the pulse widths and other possible quantum effects. In the present work, the six lowest energy electronic states of IBr~- were calculated at the MR-SO-CISD/aug-cc-pVDZ level of theory/basis set as a function of the I-Br distance. The TRPES of IBr~- were calculated in three pulse regimes: an infinitesimally short pulse, an intermediate pulse that has a temporal full width at half-maximum (fwhm) of 300 fs, which was chosen to match the experimental value, and one that is 3 times longer than the experimental value. The resulting spectra are qualitatively different, and the sources of these differences are discussed. The intermediate pulse provides very good agreement with experiment with the introduction of no adjustable parameters. The origins of the features of the experimental signal are discussed in terms of this fully quantum mechanical picture.
机译：研究了激光脉冲宽度以及其他量子力学效应在解释IBr〜-的时间分辨光电子能谱（TRPES）中的作用，并选择了与Mabbs等人的实验研究相同的条件。 [J.化学物理2005，122，174305]。在那项研究中，表明可以将最大信号频率随时间的变化与泵浦和探测激光器所访问的电子状态的势能之间的差异相关联。虽然这张经典图片很吸引人，但它基于初始I-Br间隔约为0.3？的单一轨迹。比平衡值长。此外，它不包括脉冲宽度和其他可能的量子效应的作用。在目前的工作中，在MR-SO-CISD / aug-cc-pVDZ的理论/基础水平上，计算了IBr〜-的六个最低能量电子状态，并将其作为I-Br距离的函数。 IBr〜-的TRPES是在以下三种脉冲状态下计算的：无限短脉冲，中间脉冲，其半峰（fwhm）处的时间全宽为300 fs，并选择为与实验值匹配;是实验值的3倍。所得光谱在质量上存在差异，并讨论了这些差异的来源。中间脉冲与引入无可调参数的实验非常吻合。实验信号特征的起源是根据这种全量子力学图来讨论的。

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