Dynamics of Condensed Matter and Center for Sustainable Systems Design, Chair of Theoretical Chemistry, Department of Chemistry, Paderborn University, Warburger Str. 100, 33098 Paderborn, Germany.
Paderborn Center for Parallel Computing and Institute for Lightweight Design, Paderborn University, Warburger Str. 100, D-33098 Paderborn, Germany.
Molecules. 2020 Aug 28;25(17):3939. doi: 10.3390/molecules25173939.
In the present work, we provide an electronic structure based method for the "on-the-fly" determination of vibrational sum frequency generation (v-SFG) spectra. The predictive power of this scheme is demonstrated at the air-water interface. While the instantaneous fluctuations in dipole moment are obtained using the maximally localized Wannier functions, the fluctuations in polarizability are approximated to be proportional to the second moment of Wannier functions. The spectrum henceforth obtained captures the signatures of hydrogen bond stretching, bending, as well as low-frequency librational modes.
在本工作中，我们提供了一种基于电子结构的方法，用于“实时”测定振动和频产生（v-SFG）谱。该方案的预测能力在气-水界面得到了验证。虽然使用最大局域化 Wannier 函数得到了偶极矩的瞬时涨落，但极化率的涨落近似为 Wannier 函数的二阶矩的比例。由此得到的光谱捕捉到了氢键伸缩、弯曲以及低频旋转模式的特征。
