Assessing the Effects of Orbital Relaxation and the Coherent-State Transformation in Quantum Electrodynamics Density Functional and Coupled-Cluster Theories.
Assessing the Effects of Orbital Relaxation and the Coherent-State Transformation in Quantum Electrodynamics Density Functional and Coupled-Cluster Theories.
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评估量子电动力学密度泛函和耦合团簇理论中轨道弛豫和相干态转变的影响。
DOI：
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发表时间：
2023
影响因子：
2.9
通讯作者：
A. DePrince
中科院分区：
文献类型：
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作者：
Marcus D Liebenthal;N. Vu;A. DePrince
利用时间依赖（TD）密度泛函理论（DFT）和运动方程（EOM）耦合簇（CC）理论的腔量子电动力学（QED）推广来模拟与光学腔模式强耦合的小分子。我们考虑两种类型的计算。在第一种方法（称为“松弛”）中，我们在计算的基态和激发态部分使用相干态转换的哈密顿量，并且在平均场水平上包括腔诱导的轨道松弛效应。这个过程保证了能量在后自洽场计算中是原点不变的。在第二种方法（称为“非松弛”）中，我们忽略了相干态转换和相关的轨道松弛效应。在这种情况下，基态非松弛的QED-CC计算获得适度的原点依赖，但在相干态基础上再现松弛的QED-CC结果。另一方面，基态非松弛QED平均场能量表现出严重的原点依赖性。对于在实验可实现的耦合强度下计算的激发能，松弛QED-EOM-CC和非松弛QED-EOM-CC的结果相似，而非松弛QED-EOM-CC和松弛QED-TDDFT的结果存在显著差异。首先，QED-EOM-CC和松弛QED-TDDFT都预测了与空腔模式不共振的电子态仍然会受到空腔的扰动。另一方面，不放松的QED-TDDFT无法捕捉到这种效果。其次，在大耦合强度的极限下，松弛QED-TDDFT倾向于高估Rabi分裂，而未松弛QED-TDDFT倾向于低估Rabi分裂，以松弛QED-EOM-CC的分裂为参考，松弛QED-TDDFT通常能更好地再现QED-EOM-CC的结果。
Cavity quantum electrodynamics (QED) generalizations of time-dependent (TD) density functional theory (DFT) and equation-of-motion (EOM) coupled-cluster (CC) theory are used to model small molecules strongly coupled to optical cavity modes. We consider two types of calculations. In the first approach (termed "relaxed"), we use a coherent-state-transformed Hamiltonian within the ground- and excited-state portions of the calculations, and cavity-induced orbital relaxation effects are included at the mean-field level. This procedure guarantees that the energy is origin-invariant in post-self-consistent-field calculations. In the second approach (termed "unrelaxed"), we ignore the coherent-state transformation and the associated orbital relaxation effects. In this case, ground-state unrelaxed QED-CC calculations pick up a modest origin dependence but otherwise reproduce relaxed QED-CC results within the coherent-state basis. On the other hand, a severe origin dependence manifests in ground-state unrelaxed QED mean-field energies. For excitation energies computed at experimentally realizable coupling strengths, relaxed and unrelaxed QED-EOM-CC results are similar, while significant differences emerge for unrelaxed and relaxed QED-TDDFT. First, QED-EOM-CC and relaxed QED-TDDFT both predict that electronic states that are not resonant with the cavity mode are nonetheless perturbed by the cavity. Unrelaxed QED-TDDFT, on the other hand, fails to capture this effect. Second, in the limit of large coupling strengths, relaxed QED-TDDFT tends to overestimate Rabi splittings, while unrelaxed QED-TDDFT underestimates them, given splittings from relaxed QED-EOM-CC as a reference, and relaxed QED-TDDFT generally does the better job of reproducing the QED-EOM-CC results.
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影响因子：
7
作者：
Flick, Johannes;Welakuh, Davis M.;Rubio, Angel
通讯作者：
Rubio, Angel
极化耦合团簇理论
影响因子：
4.2
作者：
Mordovina U
通讯作者：
Mordovina U
影响因子：
16.6
作者：
Campos-Gonzalez-Angulo, Jorge A.;Ribeiro, Raphael F.;Yuen-Zhou, Joel
通讯作者：
Yuen-Zhou, Joel
影响因子：
13.6
作者：
Eizner, Elad;Martinez-Martinez, Luis A.;Kena-Cohen, Stephane
通讯作者：
Kena-Cohen, Stephane
影响因子：
4.4
作者：
Tancogne-Dejean, Nicolas;Oliveira, Micael J. T.;Rubio, Angel
通讯作者：
Rubio, Angel