标题: 咨询关于OHF方法公式中的ΔEva和ΔEStokes数值的问题，谢谢 [打印本页] 作者Author: kongxp 时间: 2018-3-9 19:09 标题: 咨询关于OHF方法公式中的ΔEva和ΔEStokes数值的问题，谢谢 看了JCTC关于OHF方法H的文章(DOI: 10.1021/ct400415r)，想学习一下这个方法，便找了几个含有P元素的分子计算了一下它们的S1和T1之间的能差。不过审稿人说我算的这几个分子和JCTC中的分子在构型和其他计算条件上都不相同，为什么能直接引用这两个人数值。具体公式如下： ΔE0-0(S1)=ΔEVA(S1,OHF)-ΔEV-ΔEStokes. Here, ΔEStokes is the Stokes-shift energy loss (0.09 eV),derived from the PhCz energy difference between its 0-0′ absorption peak in cyclohexane and its 0′-0 emission peak in toluene, which includes the contribution of solvation (～0.06eV). ΔEV is the vibrational energy level difference between the 0-0′ transition and the vertical transition. If the vertical transition agrees with the 0-0′ transition, ΔEV is 0. If it corresponds to the 0-1′ transition, ΔEV is about 0.15 eV for conjugated molecules. As illustrated by the absorption and emission spectra of the studied molecules in toluene, the vertical S1 transition corresponds to the 0-1′ transition for most CT compounds, except for PIC-TRZ and CC2TA, for which small steric effects between the donor and acceptor allow a significant structural distortion and energy loss in the excited state. As listed in Table 1, if ΔEV is set to 0.15 eV, the calculated E0-0(S1) of these CT compounds shows good agreement with experiment (error ±0.03 eV), excluding PICTRZ and CC2TA.