Excited state geometry of uracil from the resonant Raman overtone spectrum using a Kramers–Kronig technique
Excited state geometry of uracil from the resonant Raman overtone spectrum using a Kramers–Kronig technique
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DOI：
10.1063/1.442759
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发表时间：
1982
影响因子：
4.4
通讯作者：
L. Chinsky;A. Laigle;W. Peticolas;P. Turpin
中科院分区：
文献类型：
--
作者：
L. Chinsky;A. Laigle;W. Peticolas;P. Turpin
本文将Blazej和Peticolas的Kramers-Kronig变换方法推广到相对于基本原理计算共振拉曼光谱中的泛音和组合带。该方法适用于尿嘧啶的紫外（257 nm）共振拉曼光谱，它显示出五个基频带和众多的泛音和组合带。该方法允许确定Δej的激发态势能最小值沿沿着第j个正常模式的五个共振拉曼活动模式的每个移动。所获得的Δej值与先前从基本原理的吸收光谱和激发轮廓获得的值相当一致。然而，不需要用于拉曼强度的实验测定的内标，也不需要假定振动线宽的任何值。吸收带的形状和谐波与基波的相对强度足以获得每个Δej的值。
The Kramers–Kronig transform technique of Blazej and Peticolas is extended to permit the calculation of overtone and combination bands in a resonant Raman spectrum relative to the fundamentals. The method is applied to the ultraviolet (257 nm) resonant Raman spectrum of uracil which exhibits five fundamental bands and numerous overtone and combination bands. The method permits the determination of Δej the shift of the excited state potential energy minimum along the jth normal mode for each of the five resonant Raman active modes. The Δej values obtained are in reasonable agreement with those obtained earlier from the absorption spectrum and excitation profiles of the fundamentals. However, no internal standard for the experimental determination of Raman intensities is required nor is it necessary to assume any value for Γ the vibronic linewidth. The shape of the absorption band and relative intensities of the harmonics to the fundamental are sufficient to obtain the value of each Δej.