Highly accurate experimentally determined energy levels of H3.

A sub-Doppler rovibrational spectroscopic survey of H3 + has been conducted which included 36 transitions in the ν2 ← 0 fundamental band, 15 transitions in the 2ν2 2←ν2 hot band, and 7 transitions in the 2ν2 2←0 overtone band, improving the uncertainties of most transitions by more than an order of magnitude to ∼4 MHz. Combination differences were used to determine relative energy levels and forbidden rotational transitions up to J = 6. A fit of the ground state to an effective Hamiltonian was used to connect ortho and para states, and to determine the absolute energy levels relative to the forbidden (0, 0) state. Ultimately, 62 rovibrational energy levels in the ground, ν2, and 2ν2 2 states were determined with ∼10 MHz uncertainty. Comparing the experimentally determined energy levels with ab initio calculations revealed an unexpected dependence of the residuals on the quantum number G.

Improving cavity-enhanced spectroscopy of molecular ions in the mid-infrared with up-conversion detection and Brewster-plate spoilers.

The performance of sensitive spectroscopic methods in the mid-IR is often limited by fringing due to parasitic etalons and the background noise in mid-infrared detectors. In particular, the technique Noise Immune Cavity Enhanced Optical Heterodyne Velocity Modulation Spectroscopy (NICE-OHVMS), which is capable of determining the frequencies of strong rovibrational transitions of molecular ions with sub-MHz uncertainty, needs improved sensitivity in order to probe weaker transitions. In this work, we have implemented up-conversion detection with NICE-OHVMS in the 3.2 - 3.9 µm region to enable the use of faster and more sensitive detectors which cover visible wavelengths. The higher bandwidth enabled detection at optimized heterodyne frequencies, which increased the overall signal from the H3+ cation by a factor of three and was able to resolve sub-Doppler features which had previously overlapped. Also, we demonstrate the effectiveness of Brewster-plate spoilers to remove fringes due to parasitic etalons in a cavity enhanced technique. Together, these improvements reduced the instrument's noise equivalent absorption to 5.9×10-11 cm-1 Hz-1/2, which represents a factor of 34 improvement in sensitivity compared to previous implementations of NICE-OHVMS. This work will enable extended high-precision spectroscopic surveys of H3+ and other important molecular ions.

Quantitative velocity modulation spectroscopy.

Velocity Modulation Spectroscopy (VMS) is arguably the most important development in the 20th century for spectroscopic study of molecular ions. For decades, interpretation of VMS lineshapes has presented challenges due to the intrinsic covariance of fit parameters including velocity modulation amplitude, linewidth, and intensity. This limitation has stifled the growth of this technique into the quantitative realm. In this work, we show that subtle changes in the lineshape can be used to help address this complexity. This allows for determination of the linewidth, intensity relative to other transitions, velocity modulation amplitude, and electric field strength in the positive column of a glow discharge. Additionally, we explain the large homogeneous component of the linewidth that has been previously described. Using this component, the ion mobility can be determined.

Tilt-tuned etalon locking for tunable laser stabilization.

Locking to a fringe of a tilt-tuned etalon provides a simple, inexpensive method for stabilizing tunable lasers. Here, we describe the use of such a system to stabilize an external-cavity quantum cascade laser; the locked laser has an Allan deviation of approximately 1 MHz over a one-second integration period, and has a single-scan tuning range of approximately 0.4 cm(-1). The system is robust, with minimal alignment requirements and automated lock acquisition, and can be easily adapted to different wavelength regions or more stringent stability requirements with minor alterations.

Communication: High precision sub-Doppler infrared spectroscopy of the HeH⁺ ion.

The hydrohelium cation, HeH(+), serves as an important benchmark for ab initio calculations that take into account non-adiabatic, relativistic, and quantum electrodynamic effects. Such calculations are capable of predicting molecular transitions to an accuracy of ~300 MHz or less. However, in order to continue to push the boundaries on these calculations, new measurements of these transitions are required. Here we measure seven rovibrational transitions in the fundamental vibrational band to a precision of ~1 MHz using the technique of Noise Immune Cavity Enhanced Optical Heterodyne Velocity Modulation Spectroscopy. These newly measured transitions are included in a fit to the rotation-vibration term values to derive refined spectroscopic constants in the v = 0 and v = 1 vibrational states, as well as to calculate rotation-vibration energy levels with high precision.

Cosmic-ray astrochemistry.

Gas-phase chemistry in the interstellar medium is driven by fast ion-molecule reactions. This, of course, demands a mechanism for ionization, and cosmic rays are the ideal candidate as they can operate throughout the majority of both diffuse and dense interstellar clouds. Aside from driving interstellar chemistry via ionization, cosmic rays also interact with the interstellar medium in ways that heat the ambient gas, produce gamma rays, and produce light element isotopes. In this paper we review the observables generated by cosmic-ray interactions with the interstellar medium, focusing primarily on the relevance to astrochemistry.

On the symmetry and degeneracy of H3(+).

The fundamental molecular ion H3(+) has impacted astronomy, chemistry, and physics, particularly since the discovery of its rovibrational spectrum. Consisting of three identical fermions, its properties are profoundly influenced by the requirements of exchange symmetry, most notably the nonexistence of its ground rotational state. Spectroscopy of H3(+) is often used to infer the relative abundances of its two nuclear spin modifications, ortho- and para-H3(+), which are important in areas as diverse as electron dissociative recombination and deuterium fractionation in cold interstellar clouds. In this paper, we explore in detail the impact of exchange symmetry on the states of H3(+), with a particular focus on the state degeneracies necessary for converting spectral transition intensities to relative abundances. We address points of confusion in the literature surrounding these issues and discuss the implications for proton-transfer reactions of H3(+) at low temperatures.

Rotationally-resolved spectroscopy of the donor bending mode of (D2O)2.

High-resolution spectra of the intramolecular bending modes of deuterated water dimer, (D2O)2, have been measured using a quantum cascade laser based cavity ringdown spectrometer. Two perpendicular bands have been observed and are assigned as the K(a) = 1 ← 0 and K(a) = 2 ← 1 bands of the bending mode of the hydrogen bond donor. The tunneling splittings in the complex are well-resolved, and it is found that excitation of the donor bend has little effect on tunneling of the hydrogen bond acceptor, but causes significant perturbations on the tunneling motion which exchanges the roles of hydrogen bond donor and acceptor. The presence of this perturbation has prevented a detailed assignment of the tunneling levels in the excited state at this time. An accurate value for the band center of the donor bend is calculated to be 1182.2 cm(-1), which is in good agreement with previous theoretical calculations performed on an ab initio potential energy surface.

Indirect rotational spectroscopy of HCO+.

Spectroscopy of the ν1 band of the astrophysically relevant ion HCO(+) is performed with an optical parametric oscillator calibrated with an optical frequency comb. The sub-MHz accuracy of this technique was confirmed by performing a combination differences analysis with the acquired rovibrational data and comparing the results to known ground-state rotational transitions. A similar combination differences analysis was performed from the same data set to calculate the previously unobserved rotational spectrum of the ν1 vibrationally excited state with precision sufficient for astronomical detection. Initial results of cavity-enhanced sub-Doppler spectroscopy are also presented and hold promise for further improving the accuracy and precision in the near future.

High-precision and high-accuracy rovibrational spectroscopy of molecular ions.

We present a versatile new instrument capable of measuring rovibrational transition frequencies of molecular ions with sub-MHz accuracy and precision. A liquid-nitrogen cooled positive column discharge cell, which can produce large column densities of a wide variety of molecular ions, is probed with sub-Doppler spectroscopy enabled by a high-power optical parametric oscillator locked to a moderate finesse external cavity. Frequency modulation (heterodyne) spectroscopy is employed to reduce intensity fluctuations due to the cavity lock, and velocity modulation spectroscopy permits ion-neutral discrimination. The relatively narrow Lamb dips are precisely and accurately calibrated using an optical frequency comb. This method is completely general as it relies on the direct measurement of absorption or dispersion of rovibrational transitions. We expect that this new approach will open up many new possibilities: from providing new benchmarks for state-of-the-art ab initio calculations to supporting astronomical observations to helping assign congested spectra by combination differences. Herein, we describe the instrument in detail and demonstrate its performance by measuring ten R-branch transitions in the ν2 band of H3(+), two transitions in the ν1 band of HCO(+), and the first sub-Doppler transition of CH5(+).

Broadly tunable mid-infrared noise-immune cavity-enhanced optical heterodyne molecular spectrometer.

The sensitive spectroscopic technique noise-immune cavity-enhanced optical heterodyne molecular spectroscopy (NICE-OHMS) has been successfully used in a variety of systems; however, no broadly tunable setup has been developed for the mid-infrared. To this end, we have integrated a difference frequency generation system into a NICE-OHMS setup. Initial optimization and characterization was completed with ro-vibrational spectroscopy of methane. Doppler-broadened frequency-modulated NICE-OHMS spectra were recorded at a sensitivity of 2×10(-7) cm(-1) Hz(-1/2). Sub-Doppler saturation signals (Lamb dips) were also observed using wavelength-modulated NICE-OHMS, achieving a sensitivity of ~6×10(-9) cm(-1) Hz(-1/2).

Noise immune cavity enhanced optical heterodyne velocity modulation spectroscopy.

The novel technique of cavity enhanced velocity modulation spectroscopy has recently been demonstrated as the first general absorption technique that allows for sub-Doppler spectroscopy of molecular ions while retaining ion-neutral discrimination. The previous experimental setup has been further improved with the addition of heterodyne detection in a NICE-OHMS setup. This improves the sensitivity by a factor of 50 while retaining sub-Doppler resolution and ion-neutral discrimination. Calibration was done with an optical frequency comb, and line centers for several N(2)(+) lines have been determined to within an accuracy of 300 kHz.

Refractive index measurements of solid parahydrogen.

Solid para-H2 is a promising gain medium for stimulated Raman scattering, due to its high number density and narrow Raman linewidth. In preparation for the design of a cw solid hydrogen Raman laser, we have made the first measurements, to our knowledge, of the index of refraction of a solid para-H2 crystal, in the wavelength range of 430-1100 nm. For a crystal stabilized at 4.4 K, this refractive index is measured to be n(p-H2)=1.130±0.001 at 514 nm. A slight, but significant, dependence on the final crystal-growth temperature is observed, with higher n(p-H2) at higher crystal-growth temperatures. Once a crystal is grown, it can be heated up to 10 K with no change in n(p-H2). The refractive index varies only slightly over the observed wavelength range, and no significant birefringence was observed.

Nuclear spin dependence of the reaction of H(3)+ with H2. I. Kinetics and modeling.

The chemical reaction H(3)(+) + H(2) → H(2) + H(3)(+) is the simplest bimolecular reaction involving a polyatomic, yet is complex enough that exact quantum mechanical calculations to adequately model its dynamics are still unfeasible. In particular, the branching fractions for the "identity," "proton hop," and "hydrogen exchange" reaction pathways are unknown, and to date, experimental measurements of this process have been limited. In this work, the nuclear-spin-dependent steady-state kinetics of the H(3)(+) + H(2) reaction is examined in detail, and employed to generate models of the ortho:para ratio of H(3)(+) formed in plasmas of varying ortho:para H(2) ratios. One model is based entirely on nuclear spin statistics, and is appropriate for temperatures high enough to populate a large number of H(3)(+) rotational states. Efforts are made to include the influence of three-body collisions in this model by deriving nuclear spin product branching fractions for the H(5)(+) + H(2) reaction. Another model, based on rate coefficients calculated using a microcanonical statistical approach, is appropriate for lower-temperature plasmas in which energetic considerations begin to compete with the nuclear spin branching fractions. These models serve as a theoretical framework for interpreting the results of laboratory studies on the reaction of H(3)(+) with H(2).

Ultra-sensitive high-precision spectroscopy of a fast molecular ion beam.

Direct spectroscopy of a fast molecular ion beam offers many advantages over competing techniques, including the generality of the approach to any molecular ion, the complete elimination of spectral confusion due to neutral molecules, and the mass identification of individual spectral lines. The major challenge is the intrinsic weakness of absorption or dispersion signals resulting from the relatively low number density of ions in the beam. Direct spectroscopy of an ion beam was pioneered by Saykally and co-workers in the late 1980s, but has not been attempted since that time. Here, we present the design and construction of an ion beam spectrometer with several improvements over the Saykally design. The ion beam and its characterization have been improved by adopting recent advances in electrostatic optics, along with a time-of-flight mass spectrometer that can be used simultaneously with optical spectroscopy. As a proof of concept, a noise-immune cavity-enhanced optical heterodyne molecular spectroscopy (NICE-OHMS) setup with a noise equivalent absorption of ~2 × 10(-11) cm(-1) Hz(-1/2) has been used to observe several transitions of the Meinel 1-0 band of N(2) (+) with linewidths of ~120 MHz. An optical frequency comb has been used for absolute frequency calibration of transition frequencies to within ~8 MHz. This work represents the first direct spectroscopy of an electronic transition in an ion beam, and also represents a major step toward the development of routine infrared spectroscopy of rotationally cooled molecular ions.

Nuclear spin dependence of the reaction of H(3)+ with H2. II. Experimental measurements.

The nuclear spin dependence of the chemical reaction H(3)(+)+ H(2) → H(2) + H(3)(+) has been studied in a hollow cathode plasma cell. Multipass infrared direct absorption spectroscopy has been employed to monitor the populations of several low-energy rotational levels of ortho- and para-H(3)(+) (o-H(3)(+) and p-H(3)(+)) in hydrogenic plasmas of varying para-H(2) (p-H(2)) enrichment. The ratio of the rates of the proton hop (k(H)) and hydrogen exchange (k(E)) reactions α ≡ k(H)/k(E) is inferred from the observed p-H(3)(+) fraction as a function of p-H(2) fraction using steady-state chemical models. Measurements have been performed both in uncooled (T(kin) ∼ 350 K) and in liquid-nitrogen-cooled (T(kin) ∼ 135 K) plasmas, marking the first time this reaction has been studied at low temperature. The value of α has been found to decrease from 1.6 ± 0.1 at 350 K to 0.5 ± 0.1 at 135 K.

Cavity-enhanced velocity modulation spectroscopy.

The spectroscopic study of molecular ions is of great importance to a variety of fields, but is challenging as ions are typically produced in plasmas containing many orders of magnitude more neutral molecules than ions. The successful technique of velocity modulation permits discrimination between ion and neutral absorption signals and has allowed the study of scores of molecular ions in the past quarter century. However, this technique has long been considered to be inappropriate for use with cavity-enhanced techniques, owing to the directional nature of the velocity modulation. Here we report what we believe to be the first demonstration of cavity-enhanced velocity modulation spectroscopy, utilizing a 2f phase-sensitive demodulation scheme. This approach offers the promise of combining very high-sensitivity spectroscopic techniques with ion-neutral discrimination, which could extend the applicability of velocity modulation to intrinsically weak transitions and to ions that cannot be produced in high abundance. The use of a cavity also permits Lamb dip spectroscopy, which offers higher resolution and precision in frequency measurements and may be useful in measuring collisional rate coefficients.

Temperature dependence of two key interstellar reactions of H(3)(+): O((3)P) + H(3)(+) and CO + H(3)(+).

The reactions of H(3)(+) with CO and with O((3)P) are the two most important reactions for the destruction of H(3)(+) in dense interstellar clouds. These two reactions are studied with sophisticated theoretical methods that should provide accurate predictions for the rate coefficients. The potential energy surfaces are studied with high-level electronic structure methods. For both reactions, simple long-range expansions are shown to be sufficiently accurate for predicting the kinetics at room temperature and lower. The kinetics is predicted from a combination of transition state theory, trajectory simulations, and master equation analysis. For the O((3)P) reaction, the interplay between the spin-orbit and the charge-quadrupole interactions is explicitly considered. For the CO reaction, we also consider the isomerization and decomposition dynamics of the two initially formed adducts. The final predictions, which are expected to be accurate to about 10 to 20%, are compared with the available experimental data. For the O((3)P) reaction, the predicted rate coefficient is accurately reproduced by the expression 1.14 x 10(-9) (T/300)(-0.156) exp(-1.41/T) cm(3) molecule(-1) s(-1) over the 5 to 400 K temperature range. For the CO reaction, the predicted rate coefficients for the H(2) + HCO(+) and H(2) + HOC(+) channels are accurately reproduced by the expressions 1.36 x 10(-9) (T/300)(-0.142) exp(3.41/T) and 8.49 x 10(-10) (T/300)(0.0661) exp(-5.21/T) cm(3) molecule(-1) s(-1), respectively, over the 10 to 400 K temperature range. These revised rate coefficient expressions imply an increase in the destruction of H(3)(+) at temperatures that are typical of dense clouds (10-30 K) by a factor of 2.5 to 3.0.

Communications: Development and characterization of a source of rotationally cold, enriched para-H3+.

In an effort to develop a source of H(3)(+) that is almost entirely in a single quantum state (J=K=1), we have successfully generated a plasma that is enriched to approximately 83% in para-H(3)(+) at a rotational temperature of 80 K. This enrichment is a result of the nuclear spin selection rules at work in hydrogenic plasmas, which dictate that only para-H(3)(+) will form from para-H(2), and that para-H(3)(+) can be converted to ortho-H(3)(+) by subsequent reaction with H(2). This is the first experimental study in which the H(2) and H(3) (+) nuclear spin selection rules have been observed at cold temperatures. The ions were produced from a pulsed solenoid valve source, cooled by supersonic expansion, and interrogated via continuous-wave cavity ringdown spectroscopy.

Dissociative recombination of highly enriched para-H3+.

The determination of the dissociative recombination rate coefficient of H(3) (+) has had a turbulent history, but both experiment and theory have recently converged to a common value. Despite this convergence, it has not been clear if there should be a difference between the rate coefficients for ortho-H(3) (+) and para-H(3) (+). A difference has been predicted theoretically and could conceivably impact the ortho:para ratio of H(3) (+) in the diffuse interstellar medium, where H(3) (+) has been widely observed. We present the results of an experiment at the CRYRING ion storage ring in which we investigated the dissociative recombination of highly enriched ( approximately 83.6%) para-H(3) (+) using a supersonic expansion source that produced ions with T(rot) approximately 60-100 K. We observed an increase in the low energy recombination rate coefficient of the enriched para-H(3) (+) by a factor of approximately 1.25 in comparison to H(3) (+) produced from normal H(2) (ortho:para=3:1). The ratio of the rate coefficients of pure para-H(3) (+) to that of pure ortho-H(3) (+) is inferred to be approximately 2 at low collision energies; the corresponding ratio of the thermal rate coefficients is approximately 1.5 at electron temperatures from 60 to 1000 K. We conclude that this difference is unlikely to have an impact on the interstellar ortho:para ratio of H(3) (+).