Vibrational Stark Effect:Fourier Grid Hamiltonian Method Study Based on W2 Potential Energy Surfaces

我们对振动Stark效应进行了理论计算研究。通过W2电子结构计算方法得到势能曲线,采用对角化Fourier格点表示的Hamiltonian矩阵数值方法,得到了高精度的非谐性振动能级。通过计算不同电场强度下一氧化碳分子的振动光谱频率,得到了振动Stark斜率,数值结果与实验值比较符合。We presented a theoretical study for the vibrational Stark effect.The potential energy curves of vibrational Hamiltonian were scanned with W2 electronic structure computational method.The anharmonic vibrational energy levels of high accuracy were obtained using diagonolization of Fourier grid Hamiltonian.As a prototypical example,we calculated the vibrational frequencies of CO molecule in series of electric field to evaluate the vibrational Stark slope.The calculated Stark tuning rate was in agreement with experimental results.国家自然科学基金项目(21373172,21321062,21533006)资