Overtone Transition 2ν1 of HCO+ and HOC+: Origin, Radiative Lifetime, Collisional Quenching.

We present spectra of the first overtone vibration transition of C-H/ O-H stretch (2ν1) in HCO+ and HOC+, recorded using a laser induced reaction action scheme inside a cryogenic 22 pole radio frequency trap. Band origins have been located at 6078.68411(19) and 6360.17630(26) cm-1, respectively. We introduce a technique based on mass selective ejection from the ion trap for recording background free action spectra. Varying the number density of the neutral action scheme reactant (CO2 and Ar, respectively) and collisional partner reactant inside the ion trap, permitted us to estimate the radiative lifetime of the state to be 1.53(34) and 1.22(34) ms, respectively, and the collisional quenching rates of HCO+(2ν1) with He, H2, and N2.

Measurements of rate coefficients of CN+, HCN+, and HNC+ collisions with H2 at cryogenic temperatures.

The experimental determination of the reaction rate coefficients for production and destruction of HCN+ and HNC+ in collision with H2 is presented. A variable-temperature, 22-pole radio frequency ion trap was used to study the reactions in the temperature range 17-250 K. The obtained rate coefficients for the reaction of CN+ and HCN+ with H2 are close to the collisional (Langevin) value, whereas that for the reaction of HNC+ with H2 is quickly decreasing with increasing temperature. The product branching ratios for the reaction of CN+ with H2 are also reported and show a notable decrease of the HNC+ product with respect to the HCN+ product with increasing temperature. These measurements have consequences for current astrochemical models of cyanide chemistry, in particular, for the HCNH+ cation.

Dissociative recombination of N2H+ ions with electrons in the temperature range of 80-350 K.

Recombination of N2H+ ions with electrons was studied using a stationary afterglow with a cavity ring-down spectrometer. We probed in situ the time evolutions of number densities of different rotational and vibrational states of recombining N2H+ ions and determined the thermal recombination rate coefficients for N2H+ in the temperature range of 80-350 K. The newly calculated vibrational transition moments of N2H+ are used to explain the different values of recombination rate coefficients obtained in some of the previous studies. No statistically significant dependence of the measured recombination rate coefficient on the buffer gas number density was observed.

Towards state selective recombination of H3+ under astrophysically relevant conditions.

We present studies on the thermalisation of H3+ ions in a cold He/Ar/H2 plasma at temperatures 30-70 K. We show that we are able to generate a rotationally thermalised H3+ ensemble with a population of rotational and nuclear spin states corresponding to a particular ion translational temperature. By varying the para-H2 fraction used in the experiment we are able to produce para-H3+ ions with fractional populations higher than those corresponding to thermodynamic values. At 35 K, only the lowest rotational states of para and ortho H3+ are populated. This is the first step towards experimental studies of electron-molecular ion recombination processes with precisely specified quantum states at astrophysically relevant temperatures.

Binary and ternary recombination of H2D(+) and HD2(+) ions with electrons at 80 K.

The recombination of deuterated trihydrogen cations with electrons has been studied in afterglow plasmas containing mixtures of helium, argon, hydrogen and deuterium. By monitoring the fractional abundances of H3(+), H2D(+), HD2(+) and D3(+) as a function of the [D2]/[H2] ratio using infrared absorption observed in a cavity ring down absorption spectrometer (CRDS), it was possible to deduce effective recombination rate coefficients for H2D(+) and HD2(+) ions at a temperature of 80 K. From pressure dependences of the measured effective recombination rate coefficients the binary and the ternary recombination rate coefficients for both ions have been determined. The inferred binary and ternary recombination rate coefficients are: αbinH2D(80 K) = (7.1 ± 4.2) × 10(-8) cm(3) s(-1), αbinHD2(80 K) = (8.7 ± 2.5) × 10(-8) cm(3) s(-1), KH2D(80 K) = (1.1 ± 0.6) × 10(-25) cm(6) s(-1) and KHD2(80 K) = (1.5 ± 0.4) × 10(-25) cm(6) s(-1).

Flowing-afterglow study of electron-ion recombination of para-H3(+) and ortho-H3(+) ions at temperatures from 60 K to 300 K.

Detailed measurements employing a combination of a cryogenic flowing afterglow with Langmuir probe (Cryo-FALP II) and a stationary afterglow with near-infrared absorption spectroscopy (SA-CRDS) show that binary electron recombination of para-H3(+) and ortho-H3(+) ions occurs with significantly different rate coefficients, (p)αbin and (o)αbin, especially at very low temperatures. The measurements cover temperatures from 60 K to 300 K. At the lowest temperature of 60 K, recombination of para-H3(+) is at least three times faster than that of ortho-H3(+) ((p)αbin=(1.8±0.4)×10(-7) cm(3) s(-1) vs. (o)αbin=(0-0 (+5))×10(-8) cm(3) s(-1)).

Binary recombination of H3(+) and D3(+) ions with electrons in plasma at 50-230 K.

The results of an experimental study of the H3(+) and D3(+) ions recombination with electrons in afterglow plasmas in the temperature range 50-230 K are presented. A flowing afterglow apparatus equipped with a Langmuir probe was used to measure the evolution of the electron number density in the decaying plasma. The obtained values of the binary recombination rate coefficient are αbinH3(+) = (6.0 ± 1.8) × 10(-8)(300/T)(0.36±0.09) cm(3) s(-1) for H3(+) ions in the temperature range 80-300 K and αbinD3(+) = (3.5 ± 1.1) × 10(-8)(300/T)(0.73±0.09) cm(3) s(-1) for D3(+) ions in the temperature range 50-300 K. This is the first measurement of the binary recombination rate coefficient of H3(+) and D3(+) ions in a plasma experiment down to 50 K.

Binary and ternary recombination of D3+ ions at 80-130 K: application of laser absorption spectroscopy.

Recombination of D(3)(+) ions with electrons at low temperatures (80-130 K) was studied using spectroscopic determination of D(3)(+) ions density in afterglow plasmas. The use of cavity ring-down absorption spectroscopy enabled an in situ determination of the abundances of the ions in plasma and the translational and the rotational temperatures of the recombining ions. Two near infrared transitions at (5792.70 ± 0.01) cm(-1) and at (5793.90 ± 0.01) cm(-1) were used to probe the number densities of the lowest ortho state and of one higher lying rotational state of the vibrational ground state of D(3)(+) ion. The results show that D(3)(+) recombination with electrons consists of the binary and the third-body (helium) assisted process. The obtained binary recombination rate coefficients are in agreement with a recent theoretical prediction for electron-ion plasma in thermodynamic equilibrium with α(bin)(80 K) = (9.2 ± 2.0) × 10(-8) cm(3) s(-1). The measured helium assisted ternary rate coefficients K(He) are in agreement with our previously measured flowing afterglow data giving a value of K(He)(80 K) = (1.2 ± 0.3) × 10(-25) cm(6) s(-1).

Binary and ternary recombination of para-H3(+) and ortho-H3(+) with electrons: state selective study at 77-200 K.

Measurements in H(3)(+) afterglow plasmas with spectroscopically determined relative abundances of H(3)(+) ions in the para-nuclear and ortho-nuclear spin states provide clear evidence that at low temperatures (77-200 K) para-H(3)(+) ions recombine significantly faster with electrons than ions in the ortho state, in agreement with a recent theoretical prediction. The cavity ring-down absorption spectroscopy used here provides an in situ determination of the para/ortho abundance ratio and yields additional information on the translational and rotational temperatures of the recombining ions. The results show that H(3)(+) recombination with electrons occurs by both binary recombination and third-body (helium) assisted recombination, and that both the two-body and three-body rate coefficients depend on the nuclear spin states. Electron-stabilized (collisional-radiative) recombination appears to make only a small contribution.