论文标题

从硼簇的热激发电子状态的形状波动和辐射

Shape fluctuations and radiation from thermally excited electronic states of boron clusters

论文作者

Höltzl, T., Ferrari, P., Janssens, E., Hansen, K.

论文摘要

已经对热形状波动对硼簇阳离子的复发荧光的影响,b $ _n^+$($ n = 9-14 $),已经进行了数值研究,并特别强调了b $ _ {13}^+$。对于该群集,使用时间依赖性密度函数理论计算基态和四个最低电子激发态的电子结构,并根据在实验相关的激发能计算出的群集的分子动力学轨迹上进行采样。 B $ _ {13}^+$的采样光学过渡矩阵元件允许从热填充的电子激发态构建其发射光谱。发现频谱很宽,至少达到0.85 eV。这与静态图片形成鲜明对比,静态图片最低的电子过渡发生在2.3 eV。低洼的电子激发产生了重复的荧光速率,其峰值为$ 4.6 \ times 10^{4} $ s $ s $^{ - 1} $,其时间平均值为$ 8 \ times 10^{3} $ s $ s $ s $ s $ s^{ - 1} $。平均值比静态结果高一个数量级,接近测得的辐射率。对于其他群集大小也发现了类似的结果。此外,计算了B $ _ {13}^+$之间的无辐射交叉和第一个电子激发态表面,与实验时间尺度相比,发现非常快,证明了热种群假设是合理的。

The effect of thermal shape fluctuations on the recurrent fluorescence of boron cluster cations, B$_N^+$ ($N=9-14$), has been investigated numerically, with a special emphasis on B$_{13}^+$. For this cluster, the electronic structures of the ground state and the four lowest electronically excited states were calculated using time-dependent density functional theory, and sampled on molecular dynamics trajectories of the cluster calculated at an experimentally relevant excitation energy. The sampled optical transition matrix elements for B$_{13}^+$ allowed to construct its emission spectrum from the thermally populated electronically excited states. The spectrum was found to be broad, reaching down to at least 0.85 eV. This contrasts strongly with the static picture, where the lowest electronic transition happens at 2.3 eV. The low-lying electronic excitations produce a strong increase in the rates of recurrent fluorescence, calculated to peak at $4.6 \times 10^{4}$ s$^{-1}$, with a time-average of $8 \times 10^{3}$ s$^{-1}$. The average value is one order of magnitude higher than the static result, approaching the measured radiation rate. Similar results were found for the other cluster sizes. Furthermore, the radiationless crossing between the ground-state and the first electronic excited state surfaces of B$_{13}^+$ was calculated, found to be very fast compared to experimental time scales, justifying the thermal population assumption.

扫码加入交流群

加入微信交流群

微信交流群二维码

扫码加入学术交流群,获取更多资源