Ab initio calculations of small hydrides including electron correlation
Ab initio calculations of small hydrides including electron correlation
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小氢化物的从头计算，包括电子关联
DOI：
10.1007/bf00551258
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发表时间：
1974
期刊：
影响因子：
--
通讯作者：
W. Kutzelnigg
中科院分区：
文献类型：
--
作者：
V. Dyczmons;W. Kutzelnigg
在SCF近似和独立电子对近似（IEPA）中包含电子相关的情况下，用高斯基计算了CH5+的五种不同结构和CH5−的一种结构。而在SCF水平上，CH5+的c5结构具有最低的能量，如果考虑相关性，c5 +和c2v结构之间的能量差可以忽略不计。与此相反，质子在大距离和中距离上接近CH4最有利于靠近CH4四面体的一个角，这意味着一个结构。在SCF水平上，CH5+分解为CH3+和H2需要~ 20kcal/mol，如果考虑相关性，则需要~ 40 kcal/mol。
Five different structures of CH5+ and one structure of CH5− are calculated using a gaussian basis both in the SCF approximation and with the inclusion of electron correlation in the independent electron pair approximation (IEPA). While on SCF level the Csstructure of CH5+ has to lowest energy, the energy difference between the Csand C2vstructures becomes negligible if correlation is included. In contrast to this the approach of a proton to CH4 at large and intermediate distances is most favorable towards a corner of the CH4 tetrahedron which means a structure. The decomposition of CH5+ into CH3+ and H2 requires ∼20kcal/mol on SCF level and ∼40 kcal/mol if correlation is included.