Micro-Solvated DMABN: Excited State Quantum Dynamics and Dual Fluorescence Spectra.
Micro-Solvated DMABN: Excited State Quantum Dynamics and Dual Fluorescence Spectra.
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DOI：
10.3390/molecules26237247
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发表时间：
2021-11-29
期刊：
影响因子：
--
通讯作者：
Worth GA
中科院分区：
文献类型：
--
作者：
Gómez S;Soysal EN;Worth GA
在这项工作中，我们报告了通过理论和光谱方法对 4-(二甲基氨基)苯甲腈 (DMABN) 在气相以及环己烷、四氢呋喃、乙腈和水溶液中激发至 L 态后的短时行为的完整分析。使用紫外吸收光谱和荧光发射光谱对 DMABN 的光谱性质进行了实验研究。该计算研究是在不同的电子结构水平上进行的，并使用可极化连续体模型（PCM）和显式溶剂分子来重现溶剂环境。此外，还使用直接动力学变分多构型高斯（DD-vMCG）方法在非绝热图中进行了激发态量子动力学模拟，这是迄今为止使用该方法进行的最大的量子动力学“即时”模拟。与参数化线性振动耦合 (LVC) 势的完全收敛多层多构型时间相关 Hartree (ML-MCTDH) 动力学的比较显示出非常相似的核波包的布居衰变和演化。环 C=C 拉伸和三种甲基倾斜模式被确定为从 L 态到 L 态内部转换的负责运动。在不同溶剂中的超快初始衰减没有观察到重大差异，但我们表明这种效应很大程度上取决于所使用的电子结构的水平。
In this work, we report a complete analysis by theoretical and spectroscopic methods of the short-time behaviour of 4-(dimethylamino)benzonitrile (DMABN) in the gas phase as well as in cyclohexane, tetrahydrofuran, acetonitrile, and water solution, after excitation to the L state. The spectroscopic properties of DMABN were investigated experimentally using UV absorption and fluorescence emission spectroscopy. The computational study was developed at different electronic structure levels and using the Polarisable Continuum Model (PCM) and explicit solvent molecules to reproduce the solvent environment. Additionally, excited state quantum dynamics simulations in the diabatic picture using the direct dynamics variational multiconfigurational Gaussian (DD-vMCG) method were performed, the largest quantum dynamics “on-the-fly” simulations performed with this method until now. The comparison with fully converged multilayer multiconfigurational time-dependent Hartree (ML-MCTDH) dynamics on parametrised linear vibronic coupling (LVC) potentials show very similar population decays and evolution of the nuclear wavepacket. The ring C=C stretching and three methyl tilting modes are identified as the responsible motions for the internal conversion from the L to the L states. No major differences are observed in the ultrafast initial decay in different solvents, but we show that this effect depends strongly on the level of electronic structure used.
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