论文标题
通过最佳轨道形状改善激发状态势能表面
Improving excited state potential energy surfaces via optimal orbital shapes
论文作者
论文摘要
我们证明，而不是诉诸于高成本动态相关方法，而是通过确保每个单个激发态使用最佳分子轨道，而无需以额外的成本来补救激发势能表面预测中的定性失败。这种方法还避免了状态平均和动态权重所需的权重选择，并在放松激发态几何形状时消除了对昂贵的波浪函数响应计算的需求。尽管多状态方法当然是近圆锥交叉点的首选，但激发态势能表面的其他特征可以从我们的单个状态方法中显着受益。在三个不同的系统中，包括双键解离，生物学相关的氨基氢解离以及氨基对环的分子电荷转移，我们表明，州特异性轨道对国家平均现状进行定性改进。
We demonstrate that, rather than resorting to high-cost dynamic correlation methods, qualitative failures in excited-state potential energy surface predictions can often be remedied at no additional cost by ensuring that optimal molecular orbitals are used for each individual excited state. This approach also avoids the weighting choices required by state-averaging and dynamic weighting and obviates their need for expensive wave function response calculations when relaxing excited state geometries. Although multi-state approaches are of course preferred near conical intersections, other features of excited-state potential energy surfaces can benefit significantly from our single state approach. In three different systems, including a double bond dissociation, a biologically relevant amino hydrogen dissociation, and an amino-to-ring intramolecular charge transfer, we show that state-specific orbitals offer qualitative improvements over the state-averaged status quo.
