Vertical transition energies vs. absorption maxima: illustration with the UV absorption spectrum of ethylene.
Vertical transition energies vs. absorption maxima: illustration with the UV absorption spectrum of ethylene.
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DOI：
10.1016/j.saa.2013.04.078
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发表时间：
2014-02
期刊：
影响因子：
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通讯作者：
B. Lasorne;J. Jornet-Somoza;H. Meyer;D. Lauvergnat;M. Robb;F. Gatti
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文献类型：
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作者：
B. Lasorne;J. Jornet-Somoza;H. Meyer;D. Lauvergnat;M. Robb;F. Gatti
我们重新审视的有效性之间的直接比较测量的吸收最大值和计算的垂直跃迁能量在0.1 eV内校准的激发态理论水平。乙烯的紫外吸收光谱说明了这一点，由于两个非常不同的原因，通常的实验值7.66 eV（V <$N）和7.11 eV（R（3s）<$N）不能直接与电子结构计算的结果进行比较。经过验证我们的理论水平对实验数据，一个新的实验参考7.28 eV的建议基准的里德伯态，和经常引用的平均跃迁能（7.80 eV）被确认为一个更安全的估计价态。
We revisit the validity of making a direct comparison between measured absorption maxima and computed vertical transition energies within 0.1 eV to calibrate an excited-state level of theory. This is illustrated on the UV absorption spectrum of ethylene for which the usual experimental values of 7.66 eV (V←N) and 7.11 eV (R(3s) ←N) cannot be compared directly to the results of electronic structure calculations for two very different reasons. After validation of our level of theory against experimental data, a new experimental reference of 7.28 eV is suggested for benchmarking the Rydberg state, and the often-cited average transition energy (7.80 eV) is confirmed as a safer estimate for the valence state.