The H3+ molecular ion plays a fundamental role in interstellar chemistry, as it initiates a network of chemical reactions that produce many molecules. In dense interstellar clouds, the H3+ abundance is understood using a simple chemical model, from which observations of H3+ yield valuable estimates of cloud path length, density and temperature. But observations of diffuse clouds have suggested that H3+ is considerably more abundant than expected from the chemical models. Models of diffuse clouds have, however, been hampered by the uncertain values of three key parameters: the rate of H3+ destruction by electrons (e-), the electron fraction, and the cosmic-ray ionization rate. Here we report a direct experimental measurement of the H3+ destruction rate under nearly interstellar conditions. We also report the observation of H3+ in a diffuse cloud (towards Persei) where the electron fraction is already known. From these, we find that the cosmic-ray ionization rate along this line of sight is 40 times faster than previously assumed. If such a high cosmic-ray flux is ubiquitous in diffuse clouds, the discrepancy between chemical models and the previous observations of H3+ can be resolved.

The branching ratios of the different reaction pathways and the overall rate coefficients of the dissociative recombination reactions of CH 3 OH 2 + and CD 3 OD 2 + have been measured at the CRYRING storage ring located in Stockholm, Sweden. Analysis of the data yielded the result that formation of methanol or deuterated methanol accounted for only 3 and 6% of the total rate in CH 3 OH 2 + and CD 3 OD 2 + , respectively. Dissociative recombination of both isotopomeres mainly involves fragmentation of the C-O bond, the major process being the three-body break-up forming CH 3 , OH and H (CD 3 , OD and D). The overall cross sections are best fitted by s = 1.2 AE 0.1 Â 10 À15 E À1.15AE0.02 cm 2 and s = 9.6 AE 0.9 Â 10 À16 E À1.20AE0.02 cm 2 for CH 3 OH 2 + and CD 3 OD 2 + , respectively. From these values thermal reaction rate coefficients of k(T) = 8.9 AE 0.9 Â 10 À7 (T/300) À0.59AE0.02 cm 3 s À1 (CH 3 OH 2 + ) and k(T) = 9.1 AE 0.9 Â 10 À7 (T/300) À0.63AE0.02 cm 3 s À1 (CD 3 OD 2 + ) can be calculated. A non-negligible formation of interstellar methanol by the previously proposed mechanism via radiative association of CH 3 + and H 2 O and subsequent dissociative recombination of the resulting CH 3 OH 2 + ion to yield methanol and hydrogen atoms is therefore very unlikely.

This paper presents the first dissociative recombination (DR) measurement of electrons with rotationally and vibrationally cold H 3 + ions. A dc discharge pinhole supersonic jet source was developed and characterized using infrared cavity ringdown spectroscopy before installation on the CRYRING ion storage ring for the DR measurements. Rotational state distributions ͑T rot ϳ 30 K͒ produced using the source were comparable to those in the diffuse interstellar medium. Our measurement of the electron energy dependence of the DR cross section showed resonances not clearly seen in experiments using rotationally hot ions, and allowed calculation of the thermal DR rate coefficient for ions at interstellar temperatures, ␣ DR ͑23 K͒ = 2.6ϫ 10 −7 cm 3 s −1 . This value is in general agreement with recent theoretical predictions by Kokoouline and Greene [Phys. Rev. A 68, 012703 (2003)]. The branching fractions of the two breakup channels, H+H+H and H+H 2 , have also been measured for rotationally and vibrationally cold H 3 + .

Branching ratios and absolute cross sections have been measured for the dissociative recombination of N 2 H + using the CRYRING ion storage ring. It has been found that the channel N 2 H + + e À ! N 2 + H accounts for only 36% of the total reaction and that the branching into the other exoergic pathway, N 2 H + + e À ! NH + N, consequently amounts to 64%. The cross section of the reaction could be fitted by the expression ¼ (2:4 AE 0:4) ; 10 À16 E À1:04AE0:02 cm 2 , which leads to a thermal reaction rate of k(T) ¼ (1:0 AE 0:2) ; 10 À7 (T =300) À0:51AE0:02 cm 3 s À1 , in favorable agreement with previous flowing afterglow Langmuir probe measurements at room temperature, although our temperature dependence is very different. The implications of these measurements for the chemistry of interstellar clouds are discussed. A standard model calculation for a dark cloud predicts a slight increase of N 2 H + in the dark clouds but a five-to sevenfold increase of the NH concentration as steady state is reached.