Crossing seams between the potential energy surfaces and possible spin inversion processes for the direct conversion of methane to methanol by the bare FeO+ species are discussed by means of the intrinsic reaction coordinate (IRC) approach. There are three crossing seams between the sextet and the quartet potential energy surfaces, and spin inversion should occur twice in the entrance and the exit channels; FeO+((6)Sigma(+)) + CH4((1)A(1)) --> OFe+(CH4)((6)A) --> TS1((4)A') --> HO-Fe+-CH3((4)A) --> TS2 ((4)A) --> Fe+(CH3OH)((4)A) --> Fe+(D-6) + CH3OH((1)A'). The first crossing seam exists in prior to TS1, a four-centered transition state for the cleavage of a C-H bond of methane. This crossing seam is the most important aspect in this reaction pathway because the molecular system should change its spin multiplicity from the sextet state to the quartet state near this crossing region, leading to a significant decrease in the barrier height of TS1 from 31.1 to 22.1 kcal/mol at the B3LYP level of density functional theory. The second crossing seam occurs in the vicinity of the hydroxy intermediate (HO-Fe+-Ch(3)), but this crossing seam would not play a significant role because the quartet IRC valley always lies below the sextet one in this region of reaction coordinate and accordingly the molecular system would preferentially move on the quartet potential energy surface. The third crossing seam exists in the exit channel in which the elimination of methanol occurs from the product complex. This crossing seam will again lead to spin inversion from the quartet to the sextet state, by which the elimination energy can be decreased from 57.2 to 37.4 kcal/mol in the FeO+/CH4 system.