AI 中文总结
本研究采用SMF-VQE算法模拟含扩展π共轭的周环反应，将活性空间选择的组合空间简化，反应能误差小于1kcal/mol，活化能误差约5-6kcal/mol，为周环反应的量子模拟提供了有效方案。
AI 中文摘要
周环反应为量子模拟提供了严格的测试，因为其机制受轨道对称性支配，且涉及相关过渡态。本研究采用变分量子本征求解器（VQE），结合先前建立的基于对称性匹配分数（SMF-VQE）的对称性引导活性空间选择方案，模拟涉及扩展π共轭与多重键的复杂体系中的狄尔斯-阿尔德（Diels-Alder）反应及烯反应（Alder-ene）。尽管当前方案得到的绝对电子能量与耦合簇方法（CCSD）计算值存在显著偏差，但对称性引导的活性空间使能量差的偏差大幅抵消。因此，预测的反应能相对于CCSD的误差小于1千卡每摩尔，活化能的重现误差约为5至6千卡每摩尔。该对称性引导方案还将活性空间选择的庞大组合空间缩减为每种反应对应的单一对称性一致选择。
英文摘要
Pericyclic reactions provide stringent tests for quantum simulations because their mechanisms are governed by orbital symmetry and involve correlated transition states. In this work, we employ the variational quantum eigensolver (VQE) combined with a previously established symmetry-guided active-space selection protocol based on symmetry-matched fractions (SMF-VQE) to simulate Diel-Alder and Alder-ene reactions in complex systems involving extended pi-conjugation and multiple bonding. Although absolute electronic energies obtained from the current protocol exhibit significant deviations from the values computed using CCSD method, the symmetry-guided active spaces yield substantial cancellation of deviations in the energy differences. As a result, reaction energies are predicted with error (relative to CCSD) less than one kcal per mol, while activation energies are reproduced within about five to six kcal per mol. The symmetry-guided protocol also reduces the large combinatorial space of active-space choices to a single symmetry-consistent selection for each reaction.
