Probing non-adiabatic conical intersections using absorption, spontaneous Raman, and femtosecond stimulated Raman spectroscopy.
Probing non-adiabatic conical intersections using absorption, spontaneous Raman, and femtosecond stimulated Raman spectroscopy.
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使用吸收、自发拉曼和飞秒受激拉曼光谱探测非绝热圆锥相交。
DOI：
10.1063/1.4843395
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发表时间：
2013
期刊：
影响因子：
--
通讯作者：
Soo
中科院分区：
文献类型：
--
作者：
M. Y. Patuwo;Soo
我们给出了双模和三模三电子态模型哈密顿量的时间框架计算的光吸收谱（ABS）、自发拉曼激发轮廓（REP）、飞秒受激拉曼光谱（FSRS）和飞秒受激拉曼激发轮廓（FSREP）结果，这些哈密顿量包含沿其两个上非绝热电子态e1（暗）和e2（亮）沿着的圆锥交叉点（CI），沿沿着非对称模式有和没有耦合（非绝热动力学）。对于每个模型中的每个电子态，存在一个耦合模式，其余模式是对称调谐模式。CI在哈密顿量中作为耦合两个上态的势项的非对角项出现，其形式为耦合模式的线性函数。我们表明：（a）Stokes和反Stokes谱线的ABS、REP和FSREP包含关于e1和e2振动带的类似信息，（B）FSRS谱的特征在于窄的固定峰和宽的移动峰，这是由来自微扰理论的三阶偏振项的不同共振分量贡献的，以及（c）在耦合到e2的e1能量区域中的Stokes FSREP中观察到非对称耦合模式的允许的第一泛音的相对强且窄的稳定带。
We present the time-frame calculated photoabsorption spectrum (ABS), spontaneous Raman excitation profile (REP), femtosecond stimulated Raman spectroscopy (FSRS) spectrum, and femtosecond stimulated Raman excitation profile (FSREP) results of a two-mode and three-mode, three-electronic-states model Hamiltonians containing conical intersections (CIs) along its two upper diabatic electronic states, e1 (dark) and e2 (bright), with and without coupling (nonadiabatic dynamics) along an asymmetric mode. For every electronic state in each model, there is one coupling mode and the rest of the modes are symmetric tuning modes. The CI appears in the Hamiltonian as off-diagonal entries to the potential term that couple the two upper states, in the form of a linear function of the coupling mode. We show that: (a) the ABS, REP, and FSREP for Stokes and anti-Stokes lines contain similar information about the e1 and e2 vibrational bands, (b) the FSRS spectra feature narrow stationary peaks and broader moving peaks contributed by the different resonant components of the third-order polarization terms from perturbation theory, and (c) a relatively strong and narrow stationary band of the allowed first overtone of the asymmetric coupling mode is observed in the Stokes FSREP in the e1 energy region with coupling to e2.
影响因子：
4.4
作者：
Lee, SY;Zhang, DH;Mathies, RA
通讯作者：
Mathies, RA
影响因子：
1.6
作者：
McCamant, DW;Kukura, P;Mathies, RA
通讯作者：
Mathies, RA