Vibronic energies and spectra of molecular dimers.
Vibronic energies and spectra of molecular dimers.
复制标题
分子二聚体的振动能量和光谱。
作者：
A. Eisfeld;L. Braun;W. Strunz;J. Briggs;J. Beck;V. Engel
我们考虑了三种不同的方法来计算由偶极-偶极相互作用耦合的分子二聚体的电子振动能级和吸收光谱。第一种方法是在单体本征态的基础上直接对角化振动哈密顿量。第二种方法是使用创建和湮灭运营商导致谐波近似的Jaynes-Cummings哈密顿量。绝热近似这个问题提供了洞察光谱行为的弱耦合和强耦合限制。第三种方法，作为检查的准确性，以前的方法，是一个数值精确解的时间相关的薛定谔方程。使用这些方法，二聚体光谱计算三个单独的染料分子，并显示出良好的协议与测量光谱。
We consider three distinct methods of calculating the vibronic levels and absorption spectra of molecular dimers coupled by dipole-dipole interactions. The first method is direct diagonalization of the vibronic Hamiltonian in a basis of monomer eigenstates. The second method is to use creation and annihilation operators leading in harmonic approximation to the Jaynes-Cummings Hamiltonian. The adiabatic approximation to this problem provides insight into spectral behavior in the weak and strong coupling limits. The third method, which serves as a check on the accuracy of the previous methods, is a numerically exact solution of the time-dependent Schrodinger equation. Using these methods, dimer spectra are calculated for three separate dye molecules and show good agreement with measured spectra.