A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Street, 664033 Irkutsk, Russia.
J Chem Phys. 2012 Jul 28;137(4):044119. doi: 10.1063/1.4737181.
A new polarization propagator approach to indirect nuclear spin-spin coupling constantans is formulated within the framework of the algebraic-diagrammatic construction (ADC) approximation and implemented at the level of the strict second-order approximation scheme, ADC(2). The ADC approach possesses transparent computational procedure operating with Hermitian matrix quantities defined with respect to physical excitations. It is size-consistent and easily extendable to higher orders via the hierarchy of available ADC approximation schemes. The ADC(2) method is tested in the first applications to HF, N(2), CO, H(2)O, HCN, NH(3), CH(4), C(2)H(2), PH(3), SiH(4), CH(3)F, and C(2)H(4). The calculated indirect nuclear spin-spin coupling constants are in good agreement with the experimental data and results of the second-order polarization propagator approximation method. The computational effort of the ADC(2) scheme scales as n(5) with respect to the number of molecular orbitals n, which makes this method promising for applications to larger molecules.
一种新的极化传播子方法被提出，用于间接核自旋-自旋耦合常数的解析理论。该方法在代数图论（ADC）近似的框架内构建，并在严格二阶近似方案 ADC(2)的水平上实现。ADC 方法具有透明的计算过程，操作的是相对于物理激发定义的厄米矩阵量。它是大小一致的，并通过可用的 ADC 近似方案的层次结构轻松扩展到更高阶。ADC(2)方法首次应用于 HF、N(2)、CO、H(2)O、HCN、NH(3)、CH(4)、C(2)H(2)、PH(3)、SiH(4)、CH(3)F 和 C(2)H(4)进行了测试。计算出的间接核自旋-自旋耦合常数与实验数据和二阶极化传播子近似方法的结果吻合良好。ADC(2)方案的计算工作量与分子轨道数 n 的 5 次方成正比，这使得该方法有望应用于更大的分子。
