DFT(B3LYP)/6-311++ G(d, p) calculations on 2-fluorobenzoic acid (2FBA) showthat the molecule has four conformers: two lowenergy conformers (forms I and II) with the carboxylic acid group assuming the cis configuration (O = C-O-H dihedral equal to 0 degrees) and two higher-energy conformers (III, IV) with a trans carboxylic group configuration. Isolation of 2FBAmonomers in argon or nitrogen matrices allows for the efficient trapping of both low-energy conformers. Narrowband selective near-IR (NIR) excitation of the 2 nu OH mode of I in both argon and N-2 matrices leads to its efficient conversion into conformer III, which is stabilized by an intramolecular O-H center dot center dot center dot F interaction. On the other hand, upon identical selective vibrational excitation of II no changes could be noticed in the argon matrix spectra, while experiments carried out on N-2 matrices showed conversion of II into III. In conformer IV (the expected direct product resulting from NIR excitation of II), the stabilizing O H center dot center dot center dot F interaction existing in III is replaced by an O-H center dot center dot center dot H repulsive interaction, which leads to a barrier separating this form from II that is about one third of that separating III from I. Under these circumstances, once formed by vibrational excitation of II, conformer IV can easily convert to the reactant species by fast tunneling, justifying the apparent inefficiency of the II -> IV conversion upon vibrational excitation of II in an argon matrix. On the other hand, the stabilization of the initially formed conformer IV by the N-2 matrix (due to OH center dot center dot center dot N-2 interactions) allows this species to survive long enough to allow the IV -> III over-the-barrier conversion to be competitive with the IV -> II tunneling, justifying the observed net conversion of the NIR excited conformer II into form III in N-2 matrix. These results demonstrate as the intramolecular local topology may decisively influence the intrinsic kinetic stability of different conformers of the same molecule. They are also a clear additional evidence of the stabilization of higher-energy trans conformers of carboxylic acids by the N-2 matrix medium that has been found before for other molecules of the same family. Published by AIP Publishing.