论文标题
环丁烯的参考能:自动化和激发态
Reference Energies for Cyclobutadiene: Automerization and Excited States
论文作者
论文摘要
环丁烯是理论化学家的众所周知的游乐场,特别适合测试地面和激发态方法。 Indeed, due to its high spatial symmetry, especially at the $D_{4h}$ square geometry but also in the $D_{2h}$ rectangular arrangement, the ground and excited states of cyclobutadiene exhibit multi-configurational characters and single-reference methods, such as adiabatic time-dependent density-functional theory (TD-DFT) or equation-of-motion coupled cluster (EOM-CC)在这种情况下众所周知,众所周知。在这项工作中,使用大量的方法和基集,我们提供了自动化屏障(定义为正方形和矩形基态能量之间的差异)和以$ d_ {2h} $ d_ {2h} $和$ d_ {4H} $ EquiLibrium结构的广泛计算研究。特别是,执行了选定的配置相互作用(SCI),多参考扰动理论(CASSCF,CASPT2和NEVPT2)和耦合群集(CCSD,CC3,CCSDT,CC4和CCSDTQ)计算。众所周知,自旋翼式形式主义在TD-DFT(与众多的交易所相关功能)和代数图解构建[ADC(2)-S,ADC(2)-X(2)-X和ADC(3)]方案中进行了测试。为自动化屏障和每个垂直过渡能量定义了理论上的最佳估计。
Cyclobutadiene is a well-known playground for theoretical chemists and is particularly suitable to test ground- and excited-state methods. Indeed, due to its high spatial symmetry, especially at the $D_{4h}$ square geometry but also in the $D_{2h}$ rectangular arrangement, the ground and excited states of cyclobutadiene exhibit multi-configurational characters and single-reference methods, such as adiabatic time-dependent density-functional theory (TD-DFT) or equation-of-motion coupled cluster (EOM-CC), are notoriously known to struggle in such situations. In this work, using a large panel of methods and basis sets, we provide an extensive computational study of the automerization barrier (defined as the difference between the square and rectangular ground-state energies) and the vertical excitation energies at $D_{2h}$ and $D_{4h}$ equilibrium structures. In particular, selected configuration interaction (SCI), multi-reference perturbation theory (CASSCF, CASPT2, and NEVPT2), and coupled-cluster (CCSD, CC3, CCSDT, CC4, and CCSDTQ) calculations are performed. The spin-flip formalism, which is known to provide a qualitatively correct description of these diradical states, is also tested within TD-DFT (combined with numerous exchange-correlation functionals) and the algebraic diagrammatic construction [ADC(2)-s, ADC(2)-x, and ADC(3)] schemes. A theoretical best estimate is defined for the automerization barrier and for each vertical transition energy.