ZEKE photoelectron spectroscopy of p-fluorophenol···H2S/H2O complexes and dissociation energy measurement using the Birge-Sponer extrapolation method.

In this work we have shown that the Birge-Sponer extrapolation method can be successfully used to determine the dissociation energies (D0) of noncovalently bound complexes. The O-H···S hydrogen-bonding interaction in the cationic state of the p-fluorophenol···H2S complex was characterized using zero kinetic energy (ZEKE) photoelectron spectroscopy. This is the first ZEKE report on the O-H···S hydrogen-bonding interaction. The adiabatic ionization energy (AIE) of the complex was determined as 65 542 cm(-1). Various intermolecular and intramolecular vibrational modes of the cation were assigned. A long progression was observed in the intermolecular stretching mode (σ) of the complex with significant anharmonicity along this mode. The anharmonicity information was used to estimate the dissociation energy (D0) in the cationic state using the Birge-Sponer extrapolation method. The D0 was estimated as 9.72 ± 1.05 kcal mol(-1). The ZEKE photoelectron spectra of analogous complex FLP···H2O was also recorded for the sake of comparison. The AIE was determined as 64 082 cm(-1). The intermolecular stretching mode in this system, however, was found to be quite harmonic, unlike that in the H2S complex. The dissociation energies of both the complexes, along with those of a few benchmark systems, such as phenol···H2O and indole···benzene complexes, were computed at various levels of theory such as MP2 at the complete basis set limit, ωB97X-D, and CCSD(T). It was found that only the ωB97X-D level values were in excellent agreement with the experimental results for the benchmark systems for the ground as well as the cationic states. The dissociation energy of the (FLP···H2S)(+) complex determined by the Birge-Sponer extrapolation was about ∼18% lower than that computed at the ωB97X-D level.