On the Accuracy of the Complete Basis Set Extrapolation for Anionic Systems: A Case Study of the Electron Affinity of Methane

• 作者: Alejandro Ramírez-Solís
• 来源期刊: 计算化学(英文)
• 学科: 化学
• 关键词: METHANE Electron AFFINITY ANION CORRELATED Calculations Complete Basis Set LIMIT
• 年，卷（期）: 2014,（2）
• 页码范围: 31-41
• 页数: 11页
• 分类号: O6

摘要

Recent experimental evidence suggests again the existence of the metastable methane anion in plasma swarms. In order to test the reliability of the complete basis set (CBS) extrapolation scheme with augmented correlation-consistent basis sets for anionic molecules, we study the evolution of the electron affinity of methane with benchmark ab initio calculations with aug-cc basis sets up to aug-cc-pV6Z + diffuse. Geometry optimizations and vibrational analysis were done at the MP2 level. The electron affinity (EA) was calculated at the MP2 and CCSD(T) levels with and without frozen core and including the extrapolations to the CBS limit. Using the aug-cc-pVnZ basis sets it is found that two non-decreasing CCSD(T) CBS limits exist for the EA (0.29 and 0.53 eV) obtained with the n = 3, 4, 5 and n = 4, 5, 6 series, respectively. A new scheme is proposed which can be generalized for very accurate quantum chemical description of molecular anions: the standard aug-cc-pVnZ basis sets can be supplemented with extra-diffuse orbitals using a simple even-tempered scheme. This yields a reliable CBS extrapolation method to develop a (discrete approximation of a) continuum anionic state near ionization, viz., one that closely matches the energy of the corresponding neutral state. These results show that CH4 has no stable anions of 2A1 symmetry, implying that plasma swarms with anionic methane consist of metastable rather than stable methane anions.