We report on the theoretical and experimental evaluation of state-selective bond activation for coherent Raman spectroscopy and control of chemical reactivity. We compare six different strategies for state-selective activation using shaped broadband femtosecond laser pulses. Results for a pair of long pulses with different wavelengths are also considered. For each of these approaches, we report on their theoretical and experimental ability to excite a desired vibrational mode while minimizing excitation of other modes including harmonics. We find that the double parabola spectral phase function gives the most intense Raman excitation with 10 cm⁻¹ selectivity with the lowest background. The sinusoidal phase function produces intense Raman excitation with high selectivity but gives a series of harmonic excitations which could hinder selectivity. Implications of this study on several fields ranging from sensing, to controlling chemical reactions, and selective excited state excitation by X-ray pulses are discussed.

中文翻译：

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状态选择性相干拉曼激发的策略比较

我们报告了相干拉曼光谱的状态选择性键激活和化学反应性控制的理论和实验评估。我们比较了使用成形宽带飞秒激光脉冲进行状态选择性激活的六种不同策略。还考虑了具有不同波长的一对长脉冲的结果。对于这些方法中的每一种，我们报告了它们激发所需振动模式同时最小化其他模式（包括谐波）的激发的理论和实验能力。我们发现双抛物线光谱相位函数给出了最强烈的拉曼激发，10 cm ^-1具有最低背景的选择性。正弦相位函数产生具有高选择性的强烈拉曼激发，但会产生一系列可能阻碍选择性的谐波激发。讨论了这项研究对传感、控制化学反应和 X 射线脉冲选择性激发态激发等多个领域的影响。