Spectroscopy Of Molecular Ions Research Articles

Infrared spectroscopy of cations in helium nanodroplets.

Here, we describe our pulsed helium droplet apparatus for spectroscopy of molecular ions. Our approach involves the doping of the droplets of about 10nm in diameter with precursor molecules, such as ethylene, followed by electron impact ionization. Droplets containing ions are irradiated by the pulsed infrared laser beam. Vibrational excitation of the embedded cations leads to the evaporation of the helium atoms in the droplets and the release of the free ions, which are detected by the quadrupole mass spectrometer. In this work, we upgraded the experimental setup by introducing an octupole RF collision cell downstream from the electron impact ionizer. The implementation of the RF ion guide increases the transmission efficiency of the ions. Filling the collision cell with additional He gas leads to a decrease in the droplet size, enhancing sensitivity to the laser excitation. We show that the spectroscopic signal depends linearly on the laser pulse energy, and the number of ions generated per laser pulse is about 100 times greater than in our previous experiments. These improvements facilitate faster and more reproducible measurements of the spectra, yielding a handy laboratory technique for the spectroscopic study of diverse molecular ions and ionic clusters at low temperature (0.4K) in He droplets.

The FELion cryogenic ion trap beam line at the FELIX free-electron laser laboratory: infrared signatures of primary alcohol cations.

The combination of a 4 K 22-pole ion trap instrument, FELion, with the widely tunable free electron lasers at the FELIX Laboratory is described in detail. It allows for wide-range infrared vibrational spectroscopy of molecular ions. In this study, the apparatus is used for infrared vibrational predissociation (IR-PD) measurements of the simple alcohol cations of methanol and ethanol as well as their protonated forms. Spectra are taken by tagging the cold molecular ions with He atoms. The infrared spectrum of protonated methanol is recorded for the first time, and the wavelength coverage for all other species is substantially extended. The bands of all spectra are analysed by comparison to ab initio calculation results at different levels of theory. Vibrational bands of different isomers and conformers (rotamers) are discussed and identified in the experimental spectra. Besides the measurement of IR-PD spectra, the method of infrared multiple photon dissociation IR-MPD is applied for some cases. Spectral narrowing due to the cold environment is observed and rotational band contours are simulated. This will help in identifying more complex species using the IR-MPD method in future measurements. Overall the IR-PD spectra reveal more bands than are observed for the IR-MPD spectra. In particular, many new bands are observed in the fingerprint region. Depletion saturation of the finite number of trapped ions is observed for the IR-PD spectra of the ethanol cation and the presence of only one isomeric species is concluded. This special feature of ion trapping spectroscopy may be used in future studies for addressing specific isomers or cleaning the ion cloud from specific isomers or conformers. In addition, the results of this study can be used as a basis to obtain high-resolution infrared vibrational and THz rotational spectra of alcohol ions in order to detect them in space.

Strong-Field Fourier Transform Vibrational Spectroscopy of D_{2}^{+} Using Few-Cycle Near-Infrared Laser Pulses.

The photoionization of D_{2} and dissociation of the resultant D_{2}^{+} are monitored by pump-probe measurements using intense near-infrared few-cycle laser pulses. The yields of D_{2}^{+} and D^{+} recorded up to the pump-probe delay time of 527ps exhibit oscillatory structures reflecting the motion of the created vibrational wave packet of D_{2}^{+}, and the Fourier transform of the data in time domain reveals the vibrational level separations with uncertainties of 0.0002-0.0097 cm^{-1}, showing a potential application of the strong-field pump-probe measurements to high-resolution spectroscopy of molecular ions.

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.

Infrared spectroscopy of molecular ions in selected rotational and spin-orbit states.

First results are presented obtained with an experimental setup developed to record IR spectra of rotationally state-selected ions. The method we use is a state-selective version of a method developed by Schlemmer et al. [Int. J. Mass Spectrom. 185, 589 (1999); J. Chem. Phys. 117, 2068 (2002)] to record IR spectra of ions. Ions are produced in specific rotational levels using mass-analyzed-threshold-ionization spectroscopy. The state-selected ions generated by pulsed-field ionization of Rydberg states of high principal quantum number (n ≈ 200) are extracted toward an octupole ion guide containing a neutral target gas. Prior to entering the octupole, the ions are excited by an IR laser. The target gas is chosen so that only excited ions react to form product ions. These product ions are detected mass selectively as a function of the IR laser wavenumber. To illustrate this method, we present IR spectra of C2H2 (+) in selected rotational levels of the (2)Πu,3/2 and (2)Πu,1/2 spin-orbit components of the vibronic ground state.

Non-destructive state detection for quantum logic spectroscopy of molecular ions.

Precision laser spectroscopy of cold and trapped molecular ions is a powerful tool in fundamental physics--used, for example, in determining fundamental constants, testing for their possible variation in the laboratory, and searching for a possible electric dipole moment of the electron. However, the absence of cycling transitions in molecules poses a challenge for direct laser cooling of the ions, and for controlling and detecting their quantum states. Previously used state-detection techniques based on photodissociation or chemical reactions are destructive and therefore inefficient, restricting the achievable resolution in laser spectroscopy. Here, we experimentally demonstrate non-destructive detection of the quantum state of a single trapped molecular ion through its strong Coulomb coupling to a well controlled, co-trapped atomic ion. An algorithm based on a state-dependent optical dipole force changes the internal state of the atom according to the internal state of the molecule. We show that individual quantum states in the molecular ion can be distinguished by the strength of their coupling to the optical dipole force. We also observe quantum jumps (induced by black-body radiation) between rotational states of a single molecular ion. Using the detuning dependence of the state-detection signal, we implement a variant of quantum logic spectroscopy of a molecular resonance. Our state-detection technique is relevant to a wide range of molecular ions, and could be applied to state-controlled quantum chemistry and to spectroscopic investigations of molecules that serve as probes for interstellar clouds.

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(+).

Efficient ground-state cooling of an ion in a large room-temperature linear Paul trap with a sub-Hertz heating rate

We demonstrate efficient resolved sideband laser cooling ($99\ifmmode\pm\else\textpm\fi{}1%$ ground-state population) of a single ${}^{40}{\mathrm{Ca}}^{+}$ ion in a large linear Paul trap (electrode spacing of 7 mm) operated at an rf drive frequency of just 3.7 MHz. For ion oscillation frequencies in the range 280--585 kHz, heating rates below or about one motional quantum per second have been measured at room temperature. The results, obtained under these unconventional sideband cooling conditions, pave the way for a range of new types of cold ion experiments, including spectroscopy of molecular ions as well as ultracold chemistry.

H 3 + at the interface between astrochemistry and astroparticle physics

The H(3)(+) molecular ion has been used by Oka and collaborators to trace the rate of ionization by cosmic rays in the interstellar medium. More energetic cosmic rays also produce diffuse γ-radiation. Now that several supernova remnants (SNRs) have been identified as γ-ray sources, it is possible to use spectroscopy of molecular ions to search for enhanced ionization rates that would pinpoint the SNRs as the accelerators of cosmic rays. It is proposed that the warm, dilute molecular gas revealed by H(3)(+) absorption in the central molecular zone of the Galaxy can also be investigated via radio recombination lines of atoms and possibly triatomic hydrogen.

Sub-Doppler mid-infrared spectroscopy of molecular ions

The technique of velocity modulation spectroscopy has recently been combined with cavity enhancement and frequency modulation methods into a technique called noise-immune cavity-enhanced optical heterodyne velocity modulation spectroscopy (NICE-OHVMS). We have implemented NICE-OHVMS with a cw-optical parametric oscillator (OPO) tunable from 3.2 to 3.9μm, and used it to record spectra of the R(1,0) and R(1,1)u transitions of the ν2 fundamental band of H3+. The high optical power and cavity enhancement enable saturation of rovibrational transitions, which allows for line center frequencies to be measured with a precision of 70kHz.

Broadband velocity modulation spectroscopy of HfF+: Towards a measurement of the electron electric dipole moment

Precision spectroscopy of trapped HfF+ will be used to search for the permanent electric dipole moment of the electron (eEDM). Prior to this study, spectroscopic information necessary for state preparation, readout, and analysis of systematic errors was not available. We have developed a powerful technique for broadband, high-resolution survey spectroscopy of molecular ions that combines cavity-enhanced direct frequency-comb spectroscopy with velocity-modulation spectroscopy (vms) and used this to measure four bands in HfF+ over a 1000cm−1 bandwidth near 800nm. Additionally, we performed targeted scans with cw-laser vms to find 15 additional bands from 9950 to 14600cm−1. We present a detailed analysis of these bands to obtain high-precision rovibrational constants, Λ-doublings, and isotope splittings for eight electronic states. We also use our results to improve theoretical predictions and discuss implications of our measurements to the eEDM experiments. These results demonstrate the application of frequency-comb and cw-vms for broadband, high-resolution spectroscopy of molecular ions.

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.

Molecular-ion trap-depletion spectroscopy of BaCl+

We demonstrate a simple technique for molecular ion spectroscopy. BaCl$^+$ molecular ions are trapped in a linear Paul trap in the presence of a room-temperature He buffer gas and photodissociated by driving an electronic transition from the ground X$^1\Sigma^+$ state to the repulsive wall of the A$^1\Pi$ state. The photodissociation spectrum is recorded by monitoring the induced trap loss of BaCl$^+$ ions as a function of excitation wavelength. Accurate molecular potentials and spectroscopic constants are determined. Comparison of the theoretical photodissociation cross-sections with the measurement shows excellent agreement. This study represents the first spectroscopic data for BaCl$^+$ and an important step towards the production of ultracold ground-state molecular ions.

Precision cavity enhanced velocity modulation spectroscopy

The new technique of cavity enhanced velocity modulation spectroscopy has been further developed, incorporating a tighter cavity to laser lock and an optical frequency comb for absolute frequency calibration. Several N 2 + transitions have been observed with much higher precision than previously possible, and transitions that were blended in earlier Doppler-limited experiments are now resolved. The full-width at half-maximum of the observed Lamb dips is ∼ 40 MHz , and appears to be dominated by a broadening due to the velocity modulation. Future extension of this technique into the mid-infrared should enable significant improvements in the sensitivity and resolution of vibrational spectroscopy of molecular ions.

IR Spectroscopy of Molecular Ions by Nonthermal Ion Ejection from Helium Nanodroplets

Infrared spectroscopy provides a means to determine the intrinsic geometrical structures of molecules. Here we present a novel spectroscopic method that uses superfluid helium nanodroplets to record IR spectra of cold molecular ions, in this particular case aniline cations. The method is based on the detection of ions that are ejected from the helium droplets following vibrational excitation of these ions. We find that spectra can be recorded with a high sensitivity and that they exhibit only a small matrix shift. The widths of the individual transitions depend on the excited vibrational level and are thought to be related to the interaction of the ion with the surrounding helium solvent shells.

Detection of single-ion spectra by Coulomb-crystal heating

The coupled motion of ions in a radiofrequency trap has been used to connect the frequency- dependent laser-induced heating of a sympathetically cooled spectroscopy ion with changes in the fluorescence of a laser-cooled control ion. This technique, sympathetic heating spectroscopy, is demonstrated using two isotopes of calcium. In the experiment, a few scattered photons from the spectroscopy ion are transformed into a large deviation from the steady-state fluorescence of the control ion. This allows us to detect an optical transition where the number of scattered photons is below our fluorescence detection limit. Possible applications of the technique to molecular ion spectroscopy are briefly discussed.

Infrared spectroscopy of organometallic ions in the gas phase: From model to real world complexes

Gas phase mid-infrared spectroscopy of molecular ions can nowadays be performed with high performance mass spectrometers coupled to free electron lasers (FEL). The wide and continuous tunability of highly intense FELs in the mid-infrared region can be exploited for performing infrared multiple photon dissociation (IRMPD) spectroscopy of molecular ions. This review will focus on gas phase IRMPD spectroscopic investigations aiming at probing the structure and the reactivity of transition metal complexes. The performance of infrared spectroscopy for characterizing the coordination mode of polydentate ligands and the spin state of the metal will be illustrated. Infrared spectroscopy has also been exploited to probe the reactivity of metal complexes, and a special attention will be given to the infrared spectroscopy of reactive intermediates.

A millimeter/submillimeter velocity modulation spectrometer for studies of molecular ions

A millimeter/submillimeter direct absorption spectrometer has been constructed that employs velocity modulation to selectively detect molecular ions. The instrument consists of a phase-locked Gunn oscillator/Schottky diode multiplier source, a gas absorption cell, and an InSb hot-electron bolometer detector. The gas cell is a single-pass system with two ring-type discharge electrodes at either end, which are connected to an rf power supply. Modulation of the ac discharge at a rate of 50kHz and phase-sensitive detection at 1f allows for selective observation of molecular ion signals and suppression of absorption from neutral species. The spectrometer can also be used in source-modulated mode, where the signal-to-noise ratio for signals generated in an ac plasma are significantly better than for dc discharges. Combining source modulation with the ac discharge for signal detection and velocity modulation for ion identification provides a powerful technique for molecular ion spectroscopy at millimeter/submillimeter wavelengths. This instrument has been used to measure the pure rotational spectra of CO+, HCO+, and SH+ with better precision than previous studies.

Laser induced reactions in a 22-pole ion trap

The method of laser induced reaction (LIR) is used to obtain an IR spectrum of bare CH5+ in the range of 250 to 3200 cm−1. The experimental spectrum compares rather favorable to theoretical predictions based on molecular dynamics simulations except for the very low frequency range below 500 cm−1. An equation relating the experimental LIR signal to the absorption coefficient and the rate of reaction of the excited species as well as a simple model for the reaction rate coefficient of the laser excited molecules is derived. A variety of LIR schemes are exemplified and their value for IR spectroscopy of molecular ions is discussed.

UV Laser Spectroscopy Using the Velocity-Modulation Technique: New Hot Bands of the B2Σ+u–X2Σ+g System of N+2

The laser absorption spectroscopy of molecular ions using the velocity-modulation technique has been employed in the UV region. The absorption source was a cw single-mode laser beam from an extra-cavity frequency doubling unit associated with a dye laser. The high-resolution spectrum of the First Negative system B2Σ+u–X2Σ+g of N+2 has been studied. The N+2 ions were produced with an electric discharge in a flowing gas mixture of He/N2. Seven vibrational bands of the Δv = 2 sequence (v′ = 2–8) have been observed in the region between 30000 and 30600 cm−1, and five of them for the first time at high resolution (v′ = 2–4, 6, 7). A set of 770 lines have been assigned; among them are several extra – lines belonging to the A2Πu–X2Σ+g system. A standard model has been used to consider the perturbations between the rovibrational levels of the B2Σ+u and A2Πu states. An improved set of deperturbed constants and effective interaction parameters were derived for the vB = 3–vA = 14 and vB = 7–vA = 20 complexes.