9-羟基苯嵌萘酮的基态能级劈裂的理论研究

当γ,μ满足一定条件时,六次函数V(R,γ)=CR⁶+2γR⁴+(γ²+μ)R²]的图像是双势阱,可用来描述质子转移,且其相应的Schrodinger方程有解析解.用此势函数结合一维双势阱模型及变分法,并用B3P86密度泛函方法在6-311G水平下计算了该分子的平衡态和过渡态的构型及能量,研究了9-羟基苯嵌萘酮的基态能级劈裂,与其它理论值相比,所得计算结果Δ_H(0)=86.13cm^-1]与实验值符合得较好.

Theoretical Study on the Ground State Energy Splitting of 9-Hydroxyphenalenone

Proton transfer is the most general and important reaction in chemistry. This work presented a sextic function to describe the potential energy surface(PES) of proton transfer. The picture of the sextic function V(R,γ)=R6+2(R4+(γ2+μ)R2 is a double-well curve, when γ and μ satisfy specific conditions. Moreover, its corresponding Schrdinger equation has exactly analytic solutions via transformation. But to the generally used quartic function V(R)=A(R4-BR2), the corresponding Schrdinger equation can′t be solved exactly. Combined this potential function with one-dimensional double-well model and variational method, the energy splitting of the ground state of 9-hydroxyphenalenone, which is a typical system of intramolecular proton transfer, was studied in this work. The structure and energy were calculated with density-functional theory(DFT) at the B3P86/6-311G level for the equilibrium configuration and the transition state. The produced barrier height was 722.85 cm-1. The energy splitting obtained ΔH(0)=86.13 cm-1 was satisfactorily compared with the experimental observations and other theoretical values.