论文标题
为振荡器强度和激发型偶极矩的基准测试TD-DFT和波浪函数方法
Benchmarking TD-DFT and Wave Function Methods for Oscillator Strengths and Excited-State Dipole Moments
论文作者
论文摘要
使用针对小化合物确定的近乎完整配置相互作用（FCI）质量的一组振荡器强度和激发状态偶极矩，我们基准了几种单参考波函数方法（CC2，CCSD，CC3，CC3，CCSDT，CCSDT，ADC（ADC（2）和ADC（3/2）和时间依赖性dftsitydstients dftsity dftctionts dftsity dftsitiond dftsitiond dftction t. （B3LYP，PBE0，M06-2X，CAM-B3LYP和$ω$ B97X-D）。我们考虑各种规程（长度，速度和混合）和形式主义的影响：运动方程（EOM）\ emph {vs}线性响应（LR），放松\ emph {vs {vs}毫无废除的轨道等。 CC2的选择比正式主义的选择更大程度地影响了振荡器强度的大小，并且与CC2相比，CCSD对此过渡性能的改善显着改善。对于激发态偶极矩，打开轨道弛豫可以显着提高ADC（2）和CC2的准确性，但在CCSD水平上效果很小。从地面到激发状态，给定方法的偶极矩上的典型误差倾向于大致三倍。有趣的是，ADC（3/2）振荡器的强度和偶极子比其ADC（2）对应物更准确，而这两个模型确实为过渡能提供了相当相似的绝对误差。关于TD-DFT，一个人发现：i）量规对所有测试功能的振荡器强度的影响相当可忽略的影响（M06-2X除外）； ii）所有功能的地面偶极子上约0.10 d的偏差； iii）对于两种考虑的激发态性能，CAM-B3LYP的总体性能更好。
Using a set of oscillator strengths and excited-state dipole moments of near full configuration interaction (FCI) quality determined for small compounds, we benchmark the performances of several single-reference wave function methods (CC2, CCSD, CC3, CCSDT, ADC(2), and ADC(3/2)) and time-dependent density-functional theory (TD-DFT) with various functionals (B3LYP, PBE0, M06-2X, CAM-B3LYP, and $ω$B97X-D). We consider the impact of various gauges (length, velocity, and mixed) and formalisms: equation of motion (EOM) \emph{vs} linear response (LR), relaxed \emph{vs} unrelaxed orbitals, etc. Beyond the expected accuracy improvements and a neat decrease of formalism sensitivy when using higher-order wave function methods, the present contribution shows that, for both ADC(2) and CC2, the choice of gauge impacts more significantly the magnitude of the oscillator strengths than the choice of formalism, and that CCSD yields a notable improvement on this transition property as compared to CC2. For the excited-state dipole moments, switching on orbital relaxation appreciably improves the accuracy of both ADC(2) and CC2, but has a rather small effect at the CCSD level. Going from ground to excited states, the typical errors on dipole moments for a given method tend to roughly triple. Interestingly, the ADC(3/2) oscillator strengths and dipoles are significantly more accurate than their ADC(2) counterparts, whereas the two models do deliver rather similar absolute errors for transition energies. Concerning TD-DFT, one finds: i) a rather negligible impact of the gauge on oscillator strengths for all tested functionals (except for M06-2X); ii) deviations of ca.~0.10 D on ground-state dipoles for all functionals; iii) the better overall performance of CAM-B3LYP for the two considered excited-state properties.
