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首页> 外文期刊>The Journal of Chemical Physics >Resonance Raman intensity analysis of a dicyanovinyl-azaadamantane: Mode-specific reorganization energies for charge-transfer and locally-excited states
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Resonance Raman intensity analysis of a dicyanovinyl-azaadamantane: Mode-specific reorganization energies for charge-transfer and locally-excited states

机译：二氰基乙烯基-氮杂金刚烷的共振拉曼强度分析：电荷转移和局部激发态的模式特定重组能

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摘要

A resonance Raman intensity analysis is performed on the intramolecular charge-transfer molecule 1-aza-adamantane-4-ylidenemalononitrile in acetonitrile solution. We explore the extent to which changes in molecular structure upon charge transfer can be obtained from resonance Raman intensity analysis, and extend the analysis method for charge-transfer excitation to take into account the possible influence of nearby locally excited states. Absolute scattering cross sections are measured at five excitation wavelengths spanning both the charge-transfer band at 324 nm and the lowest locally excited band at 231 nm, and the absorption spectra and resonance Raman intensities are modeled self-consistently to obtain the mode-specific reorganization energies accompanying electronic excitation to both states, Interference effects between the two states are considered but are found to be of minimal importance for this particular charge-transfer molecule. The reorganization parameters in terms of dimensionless normal coordinates are converted to actual bond length and bond angle changes by making use of a previously developed ground-state normal mode analysis and by comparing with electronic structure calculations on models for the donor and acceptor ends to reduce the indeterminacy in the signs of the dimensionless displacements. The geometry changes upon excitation to the LE state are dominated by lengthening of the ethylenic C=C bond, while for CT excitation the distortions are distributed over the donor, acceptor, and adamantane bridge, with a smaller C=C bond length change. (C) 1998 American Institute of Physics. [S0021-9606(98)00548-0]. [References: 56]
机译：在乙腈溶液中对分子内电荷转移分子1-氮杂-金刚烷-4-亚甲基丙二腈进行共振拉曼强度分析。我们探索了通过共振拉曼强度分析可以获得分子结构在电荷转移时发生变化的程度，并扩展了电荷转移激发的分析方法，以考虑到附近局部激发态的可能影响。在跨越324 nm的电荷转移带和231 nm的最低局部激发带的五个激发波长下测量绝对散射截面，并自相一致地对吸收光谱和共振拉曼强度进行建模，以获得特定模式的重组两种状态伴随着电子激发产生的能量，虽然考虑了两种状态之间的干扰效应，但发现对于这种特定的电荷转移分子而言，其影响最小。通过使用先前开发的基态正态模式分析，并与供体和受体端模型的电子结构计算进行比较，将无量纲法向坐标方面的重组参数转换为实际键长和键角变化。无量纲位移的迹象中的不确定性。激发到LE态时，几何形状的变化主要由烯键式C = C键的延长决定，而对于CT激发，畸变分布在施主，受体和金刚烷桥上，C = C键的长度变化较小。 （C）1998美国物理研究所。 [S0021-9606（98）00548-0]。 [参考：56]

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