Laboratorium für Physikalische Chemie, ETH Zurich, Wolfgang-Pauli-Strasse 10, 8093 Zurich, Switzerland.
J Chem Phys. 2010 Jan 28;132(4):044113. doi: 10.1063/1.3300069.
In this study, we investigate interference between several excited electronic states in resonance enhanced vibrational Raman optical activity (RROA) spectra. A gradient Franck-Condon model for the excited-state potential energy surface is applied in order to include vibronic effects in the description of the RROA intensities. Both sum-over-states and time-dependent expressions for the RROA intensities in case of close-lying excited states are given. As an example, we compare the calculated RROA and resonance Raman spectra of (S)-(+)-naproxen-OCD(3) to the experimental ones. Subsequently, we examine the excitation profiles of (S)-(+)-naproxen and study the vibration at 1611 cm(-1) in more detail in order to demonstrate how the consideration of a second excited electronic state can lead to significant changes in the RROA intensities.
在这项研究中，我们研究了共振增强振动拉曼光学活性（RROA）光谱中几个激发电子态之间的干扰。应用梯度 Franck-Condon 模型来描述激发态势能面，以在 RROA 强度的描述中包括振子效应。对于接近的激发态，给出了 RROA 强度的和态求和表达式和时间相关表达式。作为一个例子，我们将（S）-（+）-萘普生-OCD（3）的计算 RROA 和共振拉曼光谱与实验结果进行了比较。随后，我们检查了（S）-（+）-萘普生的激发谱，并更详细地研究了 1611 cm(-1)处的振动，以证明考虑第二个激发电子态如何导致 RROA 强度的显著变化。
