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Computational Characterization of “Dark” Intermediates in the Ultrafast Deactivation of Photoexcited Bilirubin
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2018-11-01 00:00:00 , DOI: 10.1021/acs.jpca.8b09392 Hari P. Upadhyaya 1
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2018-11-01 00:00:00 , DOI: 10.1021/acs.jpca.8b09392 Hari P. Upadhyaya 1
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The characterization of various intermediates in the ultrafast deactivation of photoexcited (Z,Z)-bilirubin-IXα was carried out using different computational methods. Various excited states of (Z,Z)-bilirubin-IXα and their respective vertical excitation energies were calculated using time-dependent density functional theory (TD-DFT) employing the Coulomb-attenuating method (CAM) combined with the B3LYP functional, which is known to predict accurate results on the charge transfer excitation process. Optimized geometries and absorption spectra were determined in chloroform solvent using the polarizable continuum model incorporating the integral equation formalism. The optimized geometries of different conformers of bilirubin (ZZ, ZE, EZ, and EE) along with their relative energies and vertical excitation energies were obtained. The geometry of the first excited state, S1, for the ZZ conformer was optimized using TD-DFT. The computational study suggests that excited-state intramolecular proton transfer (ESIPT) plays a major role in the deactivation process of (Z,Z)-bilirubin-IXα on a shorter time scale. The lactam–lactim tautomerism that arises from the ESIPT process gives rise to various intermediates of (Z,Z)-bilirubin-IXα. The computational results nicely corroborate the experimental findings available in the literature.
中文翻译：
光激发胆红素超快失活中“暗”中间体的计算表征
使用不同的计算方法对光激发的（Z，Z）-胆红素-IXα的超快失活中的各种中间体进行了表征。使用库仑衰减法（CAM）结合B3LYP泛函使用库仑衰减方法（CAM），通过时变密度泛函理论（TD-DFT）计算了（Z，Z）-胆红素-IXα的各种激发态及其各自的垂直激发能。已知可以预测电荷转移激发过程的准确结果。使用合并了积分方程式的可极化连续体模型，在氯仿溶剂中确定了最佳的几何形状和吸收光谱。不同构象的胆红素的最佳几何构型获得了ZZ，ZE，EZ和EE）以及它们的相对能量和垂直激发能量。使用TD-DFT优化了ZZ构象异构体的第一激发态S 1的几何形状。计算研究表明，激发态分子内质子转移（ESIPT）在较短的时间内在（Z，Z）-胆红素-IXα的失活过程中起主要作用。ESIPT过程引起的内酰胺-内酰胺互变异构现象引起了（Z，Z）-胆红素-IXα。计算结果很好地证实了文献中的实验结果。
更新日期：2018-11-01
中文翻译：
光激发胆红素超快失活中“暗”中间体的计算表征
使用不同的计算方法对光激发的（Z，Z）-胆红素-IXα的超快失活中的各种中间体进行了表征。使用库仑衰减法（CAM）结合B3LYP泛函使用库仑衰减方法（CAM），通过时变密度泛函理论（TD-DFT）计算了（Z，Z）-胆红素-IXα的各种激发态及其各自的垂直激发能。已知可以预测电荷转移激发过程的准确结果。使用合并了积分方程式的可极化连续体模型，在氯仿溶剂中确定了最佳的几何形状和吸收光谱。不同构象的胆红素的最佳几何构型获得了ZZ，ZE，EZ和EE）以及它们的相对能量和垂直激发能量。使用TD-DFT优化了ZZ构象异构体的第一激发态S 1的几何形状。计算研究表明，激发态分子内质子转移（ESIPT）在较短的时间内在（Z，Z）-胆红素-IXα的失活过程中起主要作用。ESIPT过程引起的内酰胺-内酰胺互变异构现象引起了（Z，Z）-胆红素-IXα。计算结果很好地证实了文献中的实验结果。
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