sub-Doppler Resolution Research Articles

Rotational and hyperfine analysis of the A2∑+ - X1 2π3/2 and B2∑- - X1 2π3/2 transitions of AuS

We have recorded the (0,0) and (0,0) bands of gold monosulphide (AuS) at sub-Doppler resolution by intermodulated fluorescence spectroscopy. These two red-degraded bands lie at 642.3 and 613.8 nm, respectively. The high resolution of the experiment enabled the accurate determination of the rotational, fine and 197Au hyperfine constants of the two excited states for the first time. The Fermi contact dipolar and electric quadrupolar interactions in the upper states can be understood in terms of the electronic configurations from which they arise. The signs of the spin–rotation parameters, γ(A2Σ+) = −0.080821(24) cm−1 and γ(B2Σ−) = 0.136427(20) cm−1, suggest that the fine structures of these states arise primarily by interactions with inverted 2Π states lying at higher energy.

Hyperfine constants and line separations for the S01−P13 intercombination line in neutral ytterbium with sub-Doppler resolution

Optical frequency measurements of the intercombination line $(6s^{2})\,^{1}S_{0} -(6s6p)\,^{3}P_{1}$ in the isotopes of ytterbium are carried out with the use of sub-Doppler fluorescence spectroscopy on an atomic beam. A dispersive signal is generated to which a master laser is locked, while frequency counting of an auxiliary beat signal is performed via a frequency comb referenced to a hydrogen maser. The relative separations between the lines are used to evaluate the $^{3}P_{1}$-level magnetic dipole and electric quadrupole constants for the fermionic isotopes. The center of gravity for the $^3P_1$ levels in $^{171}$Yb and $^{173}$Yb are also evaluated, where we find significant disagreement with previously reported values. These hyperfine constants provide a valuable litmus test for atomic many-body computations in ytterbium.

Accurate transition frequency list of the ν3 band of methane from sub-Doppler resolution comb-referenced spectroscopy: erratum

Accurate transition frequency list of the ν₃ band of methane from sub-Doppler resolution comb-referenced spectroscopy: erratum

Sub-Doppler electronic spectrum of the benzene-D2 complex.

Excitation spectrum of the benzene-D2 van der Waals complex in the vicinity of the S 1 ← S 0 60 1 vibronic transition of the monomer was recorded with sub-Doppler resolution by utilizing mass-selective two-color resonance-enhanced two-photon ionization. Contrary to the previous report on the benzene-H2 complex [M. Hayashi and Y. Ohshima, J. Phys. Chem. A 117, 9819 (2013)], both spin isomers correlating to para and ortho D2 (with rotational angular momentum j = 1 and 0, respectively) are identified by using a gas sample of normal D2. Three and two vibronic bands involving vdW-mode excitation were observed for the para and ortho species, respectively, in addition to their origin bands. Comparison of the results for the two spin isomers has allowed us to make unambiguous band assignments, and vibrational frequencies of all the three vdW modes have been determined for benzene-H2 and -D2. Among the three modes, the two-dimensional vdW twist is correlated to the hindered internal rotation of H2/D2 and the barrier for the internal rotation has been evaluated: 72 and 66 cm-1 for benzene-H2 and -D2, respectively. Vibronic-state dependence of the intermolecular distance between benzene and H2/D2 is discussed on the basis of precisely determined rotational constants. Homogenous line broadening has been identified for all the observed vibronic bands, and the corresponding upper-state lifetimes are determined to be in the range of 0.3-0.7 ns.

Intensity of a crossover signal relative to Lamb dips observed in Stark spectroscopy of methane

We have observed twelve triplets of two Lamb dips and a crossover signal in Stark spectroscopy of the ν3 band of methane using a comb-referenced sub-Doppler resolution spectrometer. The crossover signal consists of two crossover resonances in the Λ- and V-type three-level systems, which overlap each other in frequency under the first-order Stark shifts (Tyurikov et al., 1997). The intensity of the crossover signal relative to the Lamb dips agrees well with a simple calculation based on steady-state solutions of rate equations in weak saturation using the observed intensity ratio of the Lamb dips in the Λ-type three-level system.

High-resolution sub-Doppler infrared spectroscopy of atmospherically relevant Criegee precursor CH2I radicals: CH2 stretch vibrations and "charge-sloshing" dynamics.

The combination of a pulsed supersonic slit-discharge source and single-mode difference frequency direct absorption infrared spectroscopy permit first high resolution infrared study of the iodomethyl (CH2I) radical, with the CH2I radical species generated in a slit jet Ne/He discharge and cooled to 16 K in the supersonic expansion. Dual laser beam detection and collisional collimation in the slit expansion yield sub-Doppler linewidths (60 MHz), an absolute frequency calibration of 13 MHz, and absorbance sensitivities within a factor of two of the shot-noise limit. Fully rovibrationally resolved direct absorption spectra of the CH2 symmetric stretch mode (ν2) are obtained and fitted to a Watson asymmetric top Hamiltonian with electron spin-rotation coupling, providing precision rotational constants and spin-rotation tensor elements for the vibrationally excited state. Analysis of the asymmetric top rotational constants confirms a vibrationally averaged planar geometry in both the ground- and first-excited vibrational levels. Sub-Doppler resolution permits additional nuclear spin hyperfine structures to be observed, with splittings in excellent agreement with microwave measurements on the ground state. Spectroscopic data on CH2I facilitate systematic comparison with previous studies of halogen-substituted methyl radicals, with the periodic trends strongly correlated with the electronegativity of the halogen atom. Interestingly, we do not observe any asymmetric CH2 stretch transitions, despite S/N ≈ 25:1 on strongest lines in the corresponding symmetric CH2 stretch manifold. This dramatic reversal of the more typical 3:1 antisymmetric/symmetric CH2 stretch intensity ratio signals a vibrational transition moment poorly described by simple "bond-dipole" models. Instead, the data suggest that this anomalous intensity ratio arises from "charge sloshing" dynamics in the highly polar carbon-iodine bond, as supported by ab initio electron differential density plots and indeed consistent with observations in other halomethyl radicals and protonated cluster ions.

Extended sub-Doppler resolution spectroscopy of the ν3 band of methane

We have performed sub-Doppler resolution rovibrational spectroscopy of the ν3 band of methane (12CH4) in the mid-infrared using an optical parametric oscillator in a double-pass configuration for saturated absorption. An optical frequency comb was used for absolute frequency calibration. We have measured 22 methane line centers ranging from the P(13) to R(10) transitions with a typical uncertainty of 0.40 MHz. These measurements improve previously known transition frequencies by at least an order of magnitude.

High-resolution spectroscopy of the a4Σ−3/2 − X12Π3/2 system of gold monosulphide in the near infrared

ABSTRACTWe have recorded the a4Σ−3/2 − X12Π3/2 (0,0), (1,0), and (2,0) bands of gaseous gold monosulphide (AuS) at sub-Doppler resolution in the near-infrared region. The molecules were made in a hollow cathode discharge source by the reaction of sputtered gold with carbonyl sulphide. The high resolution of the laser excitation spectrum enabled the determination of molecular constants describing the rotational and 197Au hyperfine structure in both states, as well as the spin–rotation interaction in the a4Σ−3/2 state. The natures of the two electronic states are discussed in the context of the observed hyperfine structure.

Massively parallel sensing of trace molecules and their isotopologues with broadband subharmonic mid-infrared frequency combs

Mid-infrared spectroscopy offers supreme sensitivity for the detection of trace gases, solids and liquids based on tell-tale vibrational bands specific to this spectral region. Here, we present a new platform for mid-infrared dual-comb Fourier-transform spectroscopy based on a pair of ultra-broadband subharmonic optical parametric oscillators pumped by two phase-locked thulium-fibre combs. Our system provides fast (7 ms for a single interferogram), moving-parts-free, simultaneous acquisition of 350,000 spectral data points, spaced by a 115 MHz intermodal interval over the 3.1–5.5 µm spectral range. Parallel detection of 22 trace molecular species in a gas mixture, including isotopologues containing isotopes such as 13C, 18O, 17O, 15N, 34S, 33S and deuterium, with part-per-billion sensitivity and sub-Doppler resolution is demonstrated. The technique also features absolute optical frequency referencing to an atomic clock, a high degree of mutual coherence between the two mid-infrared combs with a relative comb-tooth linewidth of 25 mHz, coherent averaging and feasibility for kilohertz-scale spectral resolution.

Search for inversion splitting in the 3[formula omitted] band of phosphine

Sub-Doppler resolution spectroscopy of the 3ν2 band of phosphine has been carried out using a difference-frequency-generation source referenced to an optical frequency comb and a cavity-enhanced absorption cell. Three Q-branch transitions are recorded with a linewidth of 150 kHz, but no inversion splitting is observed even though it was predicted 300 kHz in Journal of Chemical Physics, vol. 145, art. No. 091102 (2016). Transition frequencies of six Q-branch transitions have been determined with an uncertainty of 6–16 kHz.

Stark effects in the ν_3 band of methane

Sub-Doppler resolution Stark-modulation spectra of 20 transitions in the ν3 band of methane have been recorded using a difference-frequency-generation source referenced to an optical frequency comb with a frequency uncertainty of a few kilohertz. First-order Stark shifts in the vibrational excited (v3=1) and ground states have been measured separately in the presence of an electric field up to 31 kV/cm. The observed spectra have been analyzed, taking into account the mixing of the vibration–rotation wave functions due to high-order vibration–rotation interactions. The permanent electric dipole moment constants induced by the vibration, rotation, and Coriolis-type terms in the v3=1 state, and those induced by rotation in the vibrational ground state, are determined as Pvib=−16.82(7) mDebye, Prot′=18.6(4) μDebye, PCor=10.4(17) μDebye, and Prot′′=24.47(12) μDebye.

Sub-Doppler resolution near-infrared spectroscopy at 1.28 μm with the noise-immune cavity-enhanced optical heterodyne molecular spectroscopy method.

We report on the sub-Doppler saturation spectroscopy of the nitrous oxide (N2O) overtone transition at 1.28μm. This measurement is performed by the noise-immune cavity-enhanced optical heterodyne molecular spectroscopy technique based on the quantum-dot (QD) laser. A high intra-cavity power, up to 10W, reaches the saturation limit of the overtone line using an optical cavity with a high finesse of 1.14(5)×105. At a pressure of several mTorr, the saturation dip is observed with a full width at half-maximum of about 2MHz and a signal-to-noise ratio of 71. To the best of our knowledge, this is the first saturation spectroscopy of molecular overtone transitions in the 1.3μm region. The QD laser is then locked to this dispersion signal with a stability of 15kHz at 1s integration time. We demonstrate the potential of the N2O as a marker because of its particularly rich spectrum at the vicinity of 1.28-1.30μm where there are several important forbidden transitions of atomic parity violation measurements and the 1.3μm O-band of optical communication.

Frequency comb assisted two-photon vibrational spectroscopy.

We report a setup for high-resolution two-photon spectroscopy using a mid-infrared continuous wave optical parametric oscillator (CW-OPO) and a near-infrared diode laser as the excitation sources, both of which are locked to fully stabilized optical frequency combs. The diode laser is directly locked to a commercial near-infrared optical frequency comb using an optical phase-locked loop. The near-infrared frequency comb is also used to synchronously pump a degenerate femtosecond optical parametric oscillator to produce a fully stabilized mid-infrared frequency comb. The beat frequency between the mid-infrared comb and the CW-OPO is then stabilized through frequency locking. We used the setup to measure a double resonant two-photon transition to a symmetric vibrational state of acetylene with a sub-Doppler resolution and high signal-to-noise ratio.

High resolution spectroscopy of jet cooled phenyl radical: The ν1 and ν2 a1 symmetry C-H stretching modes.

A series of CH stretch modes in phenyl radical (C6H5) has been investigated via high resolution infrared spectroscopy at sub-Doppler resolution (∼60 MHz) in a supersonic discharge slit jet expansion. Two fundamental vibrations of a1 symmetry, ν1 and ν2, are observed and rotationally analyzed for the first time, corresponding to in-phase and out-of-phase symmetric CH stretch excitation at the ortho/meta/para and ortho/para C atoms with respect to the radical center. The ν1 and ν2 band origins are determined to be 3073.968 50(8) cm(-1) and 3062.264 80(7) cm(-1), respectively, which both agree within 5 cm(-1) with theoretical anharmonic scaling predictions based on density functional B3LYP/6-311g++(3df,3dp) calculations. Integrated band strengths for each of the CH stretch bands are analyzed, with the relative intensities agreeing remarkably well with theoretical predictions. Frequency comparison with previous low resolution Ar-matrix spectroscopy [A. V. Friderichsen et al., J. Am. Chem. Soc. 123, 1977 (2001)] reveals a nearly uniform Δν ≈ + 10-12 cm(-1) blue shift between gas phase and Ar matrix values for ν1 and ν2. This differs substantially from the much smaller red shift (Δν ≈ - 1 cm(-1)) reported for the ν19 mode, and suggests a simple physical model in terms of vibrational mode symmetry and crowding due to the matrix environment. Finally, the infrared phenyl spectra are well described by a simple asymmetric rigid rotor Hamiltonian and show no evidence for spectral congestion due to intramolecular vibrational coupling, which bodes well for high resolution studies of other ring radicals and polycyclic aromatic hydrocarbons. In summary, the combination of slit jet discharge methods with high resolution infrared lasers enables spectroscopic investigation of even highly reactive combustion and interstellar radical intermediates under gas phase, jet-cooled (Trot ≈ 11 K) conditions.

Double resonant absorption measurement of acetylene symmetric vibrational states probed with cavity ring down spectroscopy.

A novel mid-infrared/near-infrared double resonant absorption setup for studying infrared-inactive vibrational states is presented. A strong vibrational transition in the mid-infrared region is excited using an idler beam from a singly resonant continuous-wave optical parametric oscillator, to populate an intermediate vibrational state. High output power of the optical parametric oscillator and the strength of the mid-infrared transition result in efficient population transfer to the intermediate state, which allows measuring secondary transitions from this state with a high signal-to-noise ratio. A secondary, near-infrared transition from the intermediate state is probed using cavity ring-down spectroscopy, which provides high sensitivity in this wavelength region. Due to the narrow linewidths of the excitation sources, the rovibrational lines of the secondary transition are measured with sub-Doppler resolution. The setup is used to access a previously unreported symmetric vibrational state of acetylene, ν1+ν2+ν3+ν4 (1)+ν5 (-1) in the normal mode notation. Single-photon transitions to this state from the vibrational ground state are forbidden. Ten lines of the newly measured state are observed and fitted with the linear least-squares method to extract the band parameters. The vibrational term value was measured to be at 9775.0018(45) cm(-1), the rotational parameter B was 1.162 222(37) cm(-1), and the quartic centrifugal distortion parameter D was 3.998(62) × 10(-6) cm(-1), where the numbers in the parenthesis are one-standard errors in the least significant digits.

Sub-doppler spectroscopy of sodium vapor in an ultrathin cell

The results obtained in a cell with a distance between windows on the order of several hundreds of nanometers (the so-called “nanocell”) are presented. The nanocell thickness L in the vertical direction changes from 100 to 900 nm. It is shown that the use of a nanocell with thickness L = λ/2, where λ is a laser wavelength resonant to the atomic transition D2 in sodium atoms, provides sub-Doppler resolution of transmission and fluorescence spectra.

Sub-Doppler infrared spectroscopy and formation dynamics of triacetylene in a slit supersonic expansion.

Infrared spectroscopy and formation dynamics of triacetylene are investigated in a slit jet supersonic discharge and probed with sub-Doppler resolution (≈60 MHz) on the fundamental antisymmetric CH stretch mode (ν5). The triacetylene is generated in the throat of the discharge by sequential attack of ethynyl radical with acetyelene and diacetylene: (i) HCCH → HCC + H, (ii) HCC + HCCH → HCCCCH + H, (iii) HCC + HCCCCH → HCCCCCCH + H, cooled rapidly in the slit expansion to 15 K, and probed by near shot-noise-limited absorption sensitivity with a tunable difference-frequency infrared laser. The combination of jet cooled temperatures (Trot = 15 K) and low spectral congestion permits (i) analysis of rotationally avoided crossings in the ν5 band ascribed to Coriolis interactions, as well as (ii) first detection of ν5 Π-Π hot band progressions built on the ν12 sym CC bend and definitively assigned via state-of-the-art ab initio vibration-rotation interaction parameters (αi), which make for interesting comparison with recent spectroscopic studies of Doney et al. [J. Mol. Spectrosc. 316, 54 (2015)]. The combined data provide direct evidence for significantly non-equilibrium populations in the CC bending manifold, dynamically consistent with a strongly bent radical intermediate and transition states for forming triacetylene product. The presence of intense triacetylene signals under cold, low density slit jet conditions provides support for (i) barrierless addition of HCC with HCCCCH and (ii) a high quantum yield for HCCCCCCH formation. Complete basis set calculations for energetics [CCSD(T)-f12/VnZ-f12, n = 2,3] and frequencies [CCSD(T)-f12/VdZ-f12] are presented for both radical intermediate and transition state species, predicting collision stabilization in the slit jet expansion to be competitive with unimolecular decomposition with increasing polyyne chain length.

Sub-Doppler resolution mid-infrared spectroscopy using a difference-frequency-generation source spectrally narrowed by laser linewidth transfer.

The spectral linewidth of a 3.28 μm difference-frequency-generation source has been reduced to 3.5 kHz using a laser linewidth transfer technique [Opt. Express21, 7891 (2013)]. We use an optical frequency comb with a broad servo bandwidth to transfer a narrow linewidth of a pump laser, a 1.06 μm Nd:YAG laser, to a signal laser, a 1.57 μm external-cavity laser diode. This source enables us to record the Lamb dip of the ν3 band R(2) E transition of methane with a molecular spectral linewidth of 21 kHz while the frequency axis is absolutely calibrated.

Ultra-broadband dual-comb spectroscopy across 1.0–1.9 µm

We have carried out dual-comb spectroscopy and observed in a simultaneous acquisition a 140-THz-wide spectrum from 1.0 to 1.9 µm using two fiber-based frequency combs phase-locked to each other. This ultrabroad-wavelength bandwidth is realized by setting the difference between the repetition rates of the two combs to 7.6 Hz using the sub-Hz-linewidth fiber combs. The recorded spectrum contains five vibration-rotation bands of C2H2, CH4, and H2O at different wavelengths across the whole spectrum. The determined transition frequencies of C2H2 agree with those from the previous sub-Doppler resolution measurement of individual lines using CW lasers within 2 MHz.

Sub-Doppler infrared spectroscopy of propargyl radical (H2CCCH) in a slit supersonic expansion.

The acetylenic CH stretch mode (ν1) of propargyl (H2CCCH) radical has been studied at sub-Doppler resolution (∼60 MHz) via infrared laser absorption spectroscopy in a supersonic slit-jet discharge expansion, where low rotational temperatures (Trot = 13.5(4) K) and lack of spectral congestion permit improved determination of band origin and rotational constants for the excited state. For the lowest J states primarily populated in the slit jet cooled expansion, fine structure due to the unpaired electron spin is resolved completely, which permits accurate analysis of electron spin-rotation interactions in the vibrationally excited states (εaa = - 518.1(1.8), εbb = - 13.0(3), εcc = - 1.8(3) MHz). In addition, hyperfine broadening in substantial excess of the sub-Doppler experimental linewidths is observed due to nuclear spin-electron spin contributions at the methylenic (-CH2) and acetylenic (-CH) positions, which permits detailed modeling of the fine/hyperfine structure line contours. The results are consistent with a delocalized radical spin density extending over both methylenic and acetylenic C atoms, in excellent agreement with simple resonance structures as well as ab initio theoretical calculations.