HIGH-LEVEL AB INITIO CALCULATIONS ON CH2+((2)APO((2)PI) REACTIONS

摘要

We present ab initio calculations carried out in the framework of the G2 theory on the singlet and triplet potential energy surfaces corresponding to the gas-phase between CH2+ and PO. The global minimum of both potential energy surfaces is acyclic singlet-state cation. Oxygen attachment of PO to CH2+ in a triplet configuration is accompanied by a P-O bond fission, with the result that the corresponding global minimum is an ion-dipole complex between P+(P-3) and formaldehyde. This is also consistent with the fact that our results predict the formation of formaldehyde to be highly exothermic, either as a neutral or as radical cation. Both charge-transfer processes yielding CH2(B-3(1)) or CH2((1)A(1)) are also exothermic. The formation of other carbon and oxygen containing species are endothermic. (C) 1996 John Wiley & Sons, Inc. [References: 36]