Vacuum-UV negative photoion spectroscopy of CH4

Using synchrotron radiation in the range 12-35 eV, negative ions are detected by mass spectrometry following vacuum-UV photoexcitation of methane. Ion yields for H\(^-\), CH\(^-\) and CH\(_2^-\) are recorded, the spectra of CH\(^-\) and CH\(_2^-\) for the first time. All ions display a linear dependence of signal with pressure, showing that they arise from unimolecular ion-pair dissociation. Cross sections for ion-pair formation are put onto an absolute scale by calibrating the signal strengths with those of F\(^-\) from SF\(_6\) and CF\(_4\). Following normalisation to total vacuum-UV absorption cross sections, quantum yields for anion production are reported. There is a major discrepancy in the H\(^-\) cross section with an earlier measurement, which remains unresolved. The anions arise from both direct and indirect ion-pair mechanisms. For a generic polyatomic molecule AB, the former is defined as AB \(\rightarrow\) A\(^-\) + B\(^+\) (+ neutrals), the latter as the predissociative crossing of an initially-excited Rydberg state of AB by an ion-pair state. In a separate experiment, the threshold photoelectron spectrum of the second valence band of CH\(_4\), ionisation to CH\(_4^+\) A \(^2\)A\(_1\) at 22.4 eV, is recorded with an instrumental resolution of 0.004 eV; many of the Rydberg states observed in indirect ion-pair formation converge to this state. The widths of the peaks are lifetime limited, increasing with increasing \(v\) in the \(v_1\) (a\(_1\)) vibrational ladder. They are the first direct measurement of an upper value to the dissociation rate of these levels into fragment ions