片段划分为H+和CN-,两个片段均为单重态,以反应物为例进行ETS-NOCV分析(过渡态、产物分析方法一样):
参数设置方法与ETS-NOCV计算:分析HCN体系中的H-C键,H、CN均为电中性基本一样,只更改如下:
这里因为H+、CN-都是闭壳层体系,整体也是闭壳层体系(所有电子都配对了),这种情况下,α、β电子的行为是一模一样的,所以使用Restricted就可以了。
Table 1中:
我们计算的到的: SCM - Output - Properties - Bonding Energy Decomposition:
hartree eV kcal/mol kJ/mol -------------------- ----------- ---------- ----------- Pauli Repulsion Kinetic (Delta T^0): -0.000000000000006 0.0000 0.00 0.00 Delta V^Pauli Coulomb: -0.000000070533828 0.0000 0.00 0.00 Delta V^Pauli LDA-XC: 0.000000000000001 0.0000 0.00 0.00 Delta V^Pauli GGA-Exchange: 0.000000000000000 0.0000 0.00 0.00 Delta V^Pauli GGA-Correlation: 0.000000000000000 0.0000 0.00 0.00 -------------------- ----------- ---------- ----------- Total Pauli Repulsion: -0.000000070533833 0.0000 0.00 0.00 (Total Pauli Repulsion = Delta E^Pauli in BB paper) Steric Interaction Pauli Repulsion (Delta E^Pauli): -0.000000070533833 0.0000 0.00 0.00 Electrostatic Interaction: -0.280087407012146 -7.6216 -175.76 -735.37 (Electrostatic Interaction = Delta V_elstat in the BB paper) -------------------- ----------- ---------- ----------- Total Steric Interaction: -0.280087477545979 -7.6216 -175.76 -735.37 (Total Steric Interaction = Delta E^0 in the BB paper) Orbital Interactions A: -0.295939710174702 -8.0529 -185.70 -776.99 -------------------- ----------- ---------- ----------- Total Orbital Interactions: -0.295939710174702 -8.0529 -185.70 -776.99 Alternative Decomposition Orb.Int. Kinetic: 0.425842055873293 11.5878 267.22 1118.05 Coulomb: -0.590352159617257 -16.0643 -370.45 -1549.97 XC: -0.131429606430739 -3.5764 -82.47 -345.07 -------------------- ----------- ---------- ----------- Total Orbital Interactions: -0.295939710174703 -8.0529 -185.70 -776.99 Residu (E=Steric+OrbInt+Res): 0.000000191421416 0.0000 0.00 0.00 Total Bonding Energy: -0.576026996299265 -15.6745 -361.46 -1512.36
第一组轨道相互作用对ΔEorb的贡献:154.42938 kcal/mol。如下所示 SCM - Output - Properties - ETS-NOCV:
3. Orbital Interaction Energy Contributions from each NOCV pair (in kcal/mol) 1-154.42938 2 -13.32893 3 -13.32781 4 -4.09524 Total sum: -185.446446322571 (kcal/mol)
实际上这是α、β电子共同的贡献。因为是闭壳层作用,因此α、β电子转移量相同,引起的轨道相互作用也相同。
电子转移的空间分布情况:
这是α电子转移的情况,β电子转移情况是一样的,α+β,只需要将该函数乘以2即可。View窗口菜单栏Fields - calculate,可以实现:
文献中,该图为:
NOCV orbital、NOCV density、NOCV Def(ference) density的化学直观含义,参考:ETS-NOCV理论