Radiative lifetimes of vibrationally excited H2O+ and D2O+ ions in their ground electronic state (X 2B1) have been determined using the monitor ion technique in a triple cell ion cyclotron resonance spectrometer with Fourier transform detection. The monitor reactions are proton or deuteron transfer from H(D)2O+ to CO2 and N2O. The lifetimes are corrected for collisional deactivation and reactions with the background gases occurring during the relaxation time of the ions. N2O probes all the excited vibrational levels of H2O+ and D2O+. For H2O+ only the bending modes (0,v≥1,0) contribute to the decay curve. The corresponding overall lifetime, 26.8±3 ms, is in very good agreement with the computer simulated overall lifetime including the theoretical lifetimes of Weis et al. [J. Chem. Phys. 91, 2818 (1989)] and estimated populations of the bending vibrational levels. For D2O+, the overall lifetime of the (0,v≥1,0) bending modes, 99.5±15 ms, and the lifetime of the (1,0,0) stretching mode, 27.5±4.5 ms, are observed, also in good agreement with the computer simulated and theoretical values, respectively. For both ions the overall lifetime of the (0,v≥1,0) levels may be considered as a good approximation for the radiative lifetime of the (0,1,0) level. The overall lifetimes determined with CO2 as a monitor may be attributed to the (0,v≥4,0) bending modes: 8.1±1 ms for H2O+ and 44±12 ms for D2O+. In this case, several levels having similar populations and lifetimes contribute to the decay curve, therefore the lifetimes of the individual levels cannot be determined. The agreement with computer simulated lifetimes is an indication for the validity of the theoretical lifetimes.
Radiative lifetimes of HBr+ and DBr+(2Π1/2, v=0, 1) have been determined using the monitor ion technique in a triple cell ICR spectrometer with Fourier transform detection. The experimental lifetimes corresponding to the vibrational transition v=1→0 are 10.2±1 ms and 56+12−11 ms for HBr+ and DBr+, respectively. The lifetimes calculated by a coupled electron pair approximation (CEPA) method similar to the method used previously for HF+ and HCl+ are 8.8 ms for HBr+ and 35.8 ms for DBr+, in rather good agreement with the experimental results. A comparison with previous experimental and theoretical results on hydrogen halides shows a shortening of the lifetime between the neutrals and the corresponding ions and a lengthening with isotopic substitution (H by D) as well as with substitution of F by Cl or by Br. The lifetimes corresponding to spin–orbit relaxation are very long 852+621−282 ms for HBr+ and 965+546−323 ms for DBr+. They can be considered as equal within the quite large experimental uncertainty on the contribution of collisional deactivation.
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