论文标题
在极化振动强和超肌耦合下，红外光谱的多维量子计算
Multidimensional quantum calculation of the infrared spectra under polaritonic vibrational strong and ultrastrong coupling
论文作者
论文摘要
最近的实验和理论表明，分子的基态特性和化学反应性可以在光学腔内修饰。振动的强或超腹耦合会导致形成振动极化子，这些振动偏光量通常通过红外光谱（IR）观察到。在这里，我们提供了一个理论框架，以进行分子与腔模式相互作用时进行红外光谱的多维量子模拟。以单个水分子为例，与准确的势能和偶极矩表面梳理，我们实现的腔振动振动自洽场/虚拟状态构型相互作用（CVSCF/VCI）能够在分子内部或外部腔内时提供对IR光谱的定量预测。发现共振分布的光谱特征和某些带的蓝色/红色移位与腔模式的频率和极化方向高度相关。对模拟光谱的进一步分析表明，极化强振动耦合极大地诱导了分子振动模式之间的耦合，这表明腔内分子内振动能传递可能会显着加速。
Recent experiments and theory demonstrate that the the ground state properties and chemical reactivity of molecules can be modified inside an optical cavity. The vibrational strong or ultrastrong coupling results in the formation of vibrational polaritons which are usually observed through infrared spectra (IR). Here, we provide a theoretical framework to conduct multidimensional quantum simulations of the infrared spectra when the molecule is interacting with cavity modes. Taking single water molecule as an example, combing with accurate potential energy and dipole moment surfaces, our implemented cavity vibrational self-consistent field/virtual state configuration interaction (cVSCF/VCI) is shown to be able to provide quantitative predictions of the IR spectra when the molecule is inside or outside the cavity. The spectral signatures of resonance splittings and blue/red shift of certain bands are found to be highly related with the frequency and polarization direction of the cavity modes. Further analyses of the simulated spectra shows that polaritonic strong vibrational coupling greatly induce the coupling between molecule's vibrational modes, indicating the intramolecular vibrational energy transfer may be significantly accelerated by the cavity.
