F-loss and H-loss dissociations in low-lying electronic states of the CH3F+ ion studied using multiconfiguration second-order perturbation theory

Hong-Wei Xi, Ming-Bao Huang, Bo-Zhen Chen, Wen-Zuo Li
Journal of Physical Chemistry. A 2005 October 13, 109 (40): 9149-55
Complete active space self-consistent field (CASSCF) and multiconfiguration second-order perturbation theory (CASPT2) calculations with an atomic natural orbital basis were performed for the 1(2)A'', 1(2)A', 2(2)A', 2(2)A'', and 3(2)A' (X2E, A2A1, and B2E) states of the CH3F+ ion. The 1(2)A'' state is predicted to be the ground state, and the C(s)-state energy levels are different from those of the CH3Cl+ ion. The 2(2)A' (A2A1) state is predicted to be repulsive, and the calculated adiabatic excitation energies for 2(2)A'' and 3(2)A' are very close to the experimental value for the B state. The CASPT2//CASSCF potential energy curves (PECs) were calculated for F-loss dissociation from the five C(s) states and H-loss dissociation from the 1(2)A'', 1(2)A', and 2(2)A'' states. The electronic states of the CH3+ and CH2F+ ions as the dissociation products were carefully determined by checking the energies and geometries of the asymptote products, and appearance potentials for the two ions in different states are predicted. The F-loss PEC calculations for CH3F+ indicate that F-loss dissociation occurs from the 1(2)A'', 1(2)A', and 2(2)A' states [all correlating with CH3+(X1A1')], which supports the experimental observations of direct dissociation from the X and A states, and that direct F-loss dissociation can occur from the two Jahn-Teller component states of B2E, 2(2)A'' and 3(2)A' [correlating with CH3+(1(3)A'') and CH3+(1(3)A'), respectively]. Some aspects of the 3(2)A' Cl-loss PEC of the CH3Cl+ ion are inferred on the basis of the calculation results for CH3F+. The H-loss PEC calculations for CH3F+ indicate that H-loss dissociation occurs from the 1(2)A'', 1(2)A', and 2(2)A'' states [correlating with CH2F+(1(3)A''), CH2F+(X1A1), and CH2F+(1(1)A''), respectively], which supports the observations of direct dissociation from the X and B states. As the 2(2)A' H-loss PEC of CH3Cl+, the 2(2)A' H-loss PEC of CH3F+ does not lead to H + CH2X+, but the PECs of the two ions represent different types of reactions.

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