Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996-1600, USA.
J Am Chem Soc. 2011 Sep 21;133(37):14590-2. doi: 10.1021/ja2054622. Epub 2011 Aug 24.
Experimentally measured resonance hyper-Raman (RHR) spectra spanning the S(1) ← S(0), S(2) ← S(0), and S(3) ← S(0) transitions in rhodamine 6G (R6G) have been recorded. These spectra are compared to the results of first-principles calculations of the RHR intensity that include both Franck-Condon (A-term) and non-Condon (B-term) scattering effects. Good agreement between the experimental and theoretical results is observed, demonstrating that first-principles calculations of hyper-Raman intensities are now possible for large molecules such as R6G. Such agreement indicates that RHR spectroscopy will now be a routine aid for probing multiphoton processes. This work further shows that optimization of molecular properties to enhance either A- or B-term scattering might yield molecules with significantly enhanced two-photon properties.
实验测量了跨越罗丹明 6G（R6G）的 S(1) ← S(0)、S(2) ← S(0) 和 S(3) ← S(0)跃迁的共振超拉曼（RHR）光谱。这些光谱与包括 Franck-Condon（A 项）和非 Franck-Condon（B 项）散射效应的 RHR 强度的第一性原理计算结果进行了比较。实验结果与理论结果吻合较好，表明现在可以对 R6G 等大分子进行超拉曼强度的第一性原理计算。这种一致性表明，RHR 光谱现在将成为探测多光子过程的常规辅助手段。这项工作进一步表明，优化分子性质以增强 A 项或 B 项散射，可能会产生具有显著增强的双光子性质的分子。
