Thodika Mushir, Mackouse Nathan, Matsika Spiridoula
Department of Chemistry, Temple University, 1901 N 13th Street, Philadelphia, Pennsylvania 19122, United States.
J Phys Chem A. 2020 Oct 29;124(43):9011-9020. doi: 10.1021/acs.jpca.0c07904. Epub 2020 Oct 20.
Two-particle one-hole (2p-1h) resonances are elusive to accurate characterization, their decay to the neutral state being a two-electron process. Although in limited cases, single reference methods can be used, a proper description of a 2p-1h resonant state entails a multiconfigurational treatment of the reference wavefunction. In this work, we test the performance of the orbital stabilization method to characterize the 2p-1h resonances found in water and benzene. We employ a set of two multireference approaches, namely, the restricted active space self-consistent field and the multireference configuration interaction, as well as the single reference method equation of motion for electron attachment coupled-cluster with singles and doubles, in the case of benzene. We further explore the resonant channel mixing in benzene between the B shape resonance and 2p-1h resonance, a phenomenon which has been explored quite often in experimental studies.
两粒子一空穴（2p-1h）共振难以得到准确表征，其衰变为中性态是一个双电子过程。尽管在有限的情况下可以使用单参考方法，但对2p-1h共振态的恰当描述需要对参考波函数进行多组态处理。在这项工作中，我们测试了轨道稳定化方法表征在水和苯中发现的2p-1h共振的性能。我们采用了两种多参考方法，即受限活性空间自洽场和多参考组态相互作用，在苯的情况下还采用了单参考方法——含单双激发的电子附着耦合簇运动方程。我们进一步探究了苯中B形共振和2p-1h共振之间的共振通道混合，这一现象在实验研究中经常被探讨。
