Optical-optical Double Resonance Spectroscopy Research Articles

Sub-Doppler optical-optical double-resonance spectroscopy using a cavity-enhanced frequency comb probe

Accurate parameters of molecular hot-band transitions, i.e., those starting from vibrationally excited levels, are needed to accurately model high-temperature spectra in astrophysics and combustion, yet laboratory spectra measured at high temperatures are often unresolved and difficult to assign. Optical-optical double-resonance (OODR) spectroscopy allows the measurement and assignment of individual hot-band transitions from selectively pumped energy levels without the need to heat the sample. However, previous demonstrations lacked either sufficient resolution, spectral coverage, absorption sensitivity, or frequency accuracy. Here we demonstrate OODR spectroscopy using a cavity-enhanced frequency comb probe that combines all these advantages. We detect and assign sub-Doppler transitions in the spectral range of the 3ν3 ← ν3 resonance of methane with frequency precision and sensitivity more than an order of magnitude better than before. This technique will provide high-accuracy data about excited states of a wide range of molecules that is urgently needed for theoretical modeling of high-temperature data and cannot be obtained using other methods.

Optical-optical double resonance spectroscopy of Rb 5D3/2,5/2 in magnetic fields

We have investigated the optical-optical double resonance (OODR) spectroscopy of 87Rb for transition 5S1/2 → 5P3/2 → 5D3/2,5/2 in magnetic fields. Unlike the electromagnetically induced transparency (EIT) spectroscopy of the transition to high Rydberg states (Opt Express, 25(2017)33575), the spectral observation to this low excited state remains much discrepancy compared to the theory simulation as the strong coupling between 5P3/2 and 5D3/2,5/2 leads to a state-dependent spectral broadening due to double resonance optical pumping (DROP) effect. Instead, the OODR method employs a weak optical coupling between these two states, serving as probe, where the spectral broadening can be ignored. We experimentally record the Zeeman-splitting spectrum of 87Rb to 5D3/2 and 5D5/2 in magnetic fields by OODR and the observed spectra are well in accordance with the theoretical calculation. It shows OODR is more suitable to investigate the high resolution spectroscopy of the excited state when the relaxation in DROP can't be neglected.

Analysis of the hyperfine structure of the [formula omitted][formula omitted] and [formula omitted] states of [formula omitted]Li[formula omitted]Li

We report on our theoretical analysis of the hyperfine splitting in the spectra of the 13Δg,23Πg, and 33Σg+ triplet states of 6Li7Li, which were experimentally observed in 2002 (Li et al.) by means of Perturbation Facilitated Optical-Optical Double Resonance (PFOODR) spectroscopy. In our previous work, both homonuclear and heteronuclear molecules were analyzed. However, in this work, we theoretically investigate an isotope-substituted homonuclear molecule for the first time and demonstrate the application of our approach to this case. In our model, we reproduce the major stages of the excitation–de-excitation schemes by considering the mixed nature of the intermediate A1Σu+∼b3ΠΩu singlet–triplet states, whereby the three components of the Ω=0,1,2 basis states might contribute to the hyperfine splitting. We compute the contributions from all components of the mixed states. We present physical models for all triplet states under study, along with the obtained parameters of the analyzed molecular system and the simulation results. Additionally, we describe the principal steps of the computational algorithm in detail.

Measurement and assignment of double-resonance transitions to the 8900–9100- cm−1 levels of methane

Optical-optical double-resonance spectroscopy with a continuous wave pump and frequency comb probe allows measurement of sub-Doppler transitions to highly excited molecular states over a wide spectral range with high frequency accuracy. We report on assessment and characterization of sub-Doppler double-resonance transitions in methane measured using a 3.3-$\ensuremath{\mu}\mathrm{m}$ continuous wave optical parametric oscillator as a pump and a 1.67-$\ensuremath{\mu}\mathrm{m}$ frequency comb as a probe. The comb spectra were recorded using a Fourier transform spectrometer with comb-mode-limited resolution. With the pump tuned to nine different transitions in the ${\ensuremath{\nu}}_{3}$ fundamental band, we detected 36 ladder-type transitions to the $3{\ensuremath{\nu}}_{3}$ overtone band region, and 18 V-type transitions to the $2{\ensuremath{\nu}}_{3}$ overtone band. We describe in detail the experimental approach and the pump stabilization scheme, which currently limits the frequency accuracy of the measurement. We present the data analysis procedure used to extract the frequencies and intensities of the probe transitions for parallel and perpendicular relative pump-probe polarization. We compare the center frequencies and relative intensities of the ladder-type transitions to theoretical predictions from the TheoReTS and ExoMol line lists, demonstrating good agreement with TheoReTS.

Optical-optical double-resonance dual-comb spectroscopy with pump-intensity modulation.

We apply an intensity-modulation technique to dual-comb spectroscopy to improve its detection sensitivity. The scheme is demonstrated via Doppler-free optical-optical double-resonance spectroscopy of Rb by modulating the intensity of a pump laser with frequencies set at rates 3 times lower and 50,000 times higher than the difference in the repetition rates of the two frequency combs. The signal-to-noise ratios are enhanced by 3 and 6 times for slow and fast modulations, respectively, compared to those of conventional dual-comb spectroscopy without any intensity modulation. The technique is widely applicable to pump-probe spectroscopy with dual-comb spectroscopy and provides high detection sensitivity.

Measurement of the Na2 51Σg+→A1Σu+ and 61Σg+→A1Σu+ transition dipole moments using optical-optical double resonance and Autler-Townes spectroscopy.

Accurate knowledge of transition dipole moment matrix elements is crucial since important parameters associated with the interaction of light with matter, such as emission and absorption line intensities, lifetimes, and Einstein coefficients, depend on these matrix elements. We report here an experimental study of the Na2 51Σg+↔A1Σu+ and 61Σg+↔A1Σu+ electronic transition dipole moments and their dependence on internuclear distance. We have measured absolute transition dipole matrix elements for ro-vibrational transitions of the Na2 51Σg+↔A1Σu+ and 61Σg+↔A1Σu+ electronic transitions using Autler-Townes and optical-optical double resonance spectroscopy, and we compare the results to ab initio theoretical values [A. Sanli et al., J. Chem. Phys. 143, 104304 (2015)].

Rotationally inelastic collisions of excited NaK and NaCs molecules with noble gas and alkali atom perturbers.

We report measurements of rate coefficients at T ≈ 600 K for rotationally inelastic collisions of NaK molecules in the 2(A)1Σ+ electronic state with helium, argon, and potassium atom perturbers. Several initial rotational levels J between 14 and 44 were investigated. Collisions involving molecules in low-lying vibrational levels (v = 0, 1, and 2) of the 2(A)1Σ+ state were studied using Fourier-transform spectroscopy. Collisions involving molecules in a higher vibrational level, v = 16, were studied using pump/probe, optical-optical double resonance spectroscopy. In addition, polarization spectroscopy measurements were carried out to study the transfer of orientation in these collisions. Many, but not all, of the measurements were carried out in the "single-collision regime" where more than one collision is unlikely to occur within the lifetime of the excited molecule. The analysis of the experimental data, which is described in detail, includes an estimate of effects of multiple collisions on the reported rate coefficients. The most significant result of these experiments is the observation of a strong propensity for ΔJ = even transitions in collisions involving either helium or argon atoms; the propensity is much stronger for helium than for argon. For the initial rotational levels studied experimentally, almost all initial orientation is preserved in collisions of NaK 2(A)1Σ+ molecules with helium. Roughly between 1/3 and 2/3 of the orientation is preserved in collisions with argon, and almost all orientation is destroyed in collisions with potassium atoms. Complementary measurements on rotationally inelastic collisions of NaCs 2(A)1Σ+ with argon do not show a ΔJ = even propensity. The experimental results are compared with new theoretical calculations of collisions of NaK 2(A)1Σ+ with helium and argon. The calculations are in good agreement with the absolute magnitudes of the experimentally determined rate coefficients and accurately reproduce the very strong propensity for ΔJ = even transitions in helium collisions and the less strong propensity for ΔJ = even transitions in argon collisions. The calculations also show that collisions with helium are less likely to destroy orientation than collisions with argon, in agreement with the experimental results.

Doppler-free dual-comb spectroscopy of Rb using optical-optical double resonance technique.

We present a Doppler-free high-resolution dual-comb spectroscopy technique in which a dual-comb system is employed to perform optical-optical double-resonance (OODR) spectroscopy. In our experimental study, Doppler-free high-resolution and high-frequency-accuracy broadband measurements were realized using the proposed OODR dual-comb spectroscopic technique, which does not require high-power-per-mode frequency combs. We observed fully resolved hyperfine spectra of 5P3/2 - 4D5/2, 4D3/2 transitions of Rb at 1530 nm and precisely determined the absolute frequencies of the transitions, with an uncertainty of less than 1 MHz. The variations of the OODR spectral line shapes due to power broadening and alignment and the effects of polarization on the dual-comb OODR spectra were also analyzed. This study provides a widely applicable technique for Doppler-free dual-comb spectroscopy of various gaseous species.

Observation of the5p3/2→6p3/2electric-dipole-forbidden transition in atomic rubidium using optical-optical double-resonance spectroscopy

Direct evidence of excitation of the 5p3/2 -> 6p3/2 electric dipole forbidden transition in atomic rubidium is presented. The experiments were performed in a room temperature rubidium cell with continuous wave extended cavity diode lasers. Optical-optical double resonance spectroscopy with counterpropagating beams allows the detection of the non-dipole transition free of Doppler broadening. The 5p3/2 state is prepared by excitation with a laser locked to the maximum F cyclic transition of the D2 line, and the forbidden transition is produced by excitation with a 911 nm laser. Production of the forbidden transition is monitored by detection of the 420 nm fluorescence that results from decay of the 6p3/2 state. Spectra with three narrow lines (~ 13 MHz FWHM) with the characteristic F - 1, F and F + 1 splitting of the 6p3/2 hyperfine structure in both rubidium isotopes were obtained. The results are in very good agreement with a direct calculation that takes into account the 5s -> 5p3/2 preparation dynamics, the 5p3/2 -> 6p3/2 non-dipole excitation geometry and the 6p3/2 -> 5s1/2 decay. The comparison also shows that the electric dipole forbidden transition is a very sensitive probe of the preparation dynamics.

Perturbation-facilitated detection of the first quintet-quintet band in C2

The first high-spin transition in C2 (1 (5)Πu - 1 (5)Πg) is observed by perturbation-facilitated optical-optical double resonance spectroscopy. The experiment is performed by applying unfolded two-color resonant four-wave mixing. C2 radicals in the initial a (3)Πu, v = 5 state are produced by using a discharge source in a molecular beam environment. The final quintet state is excited via intermediate "gateway" states exhibiting both substantial triplet and quintet character due to a perturbation between the 1 (5)Πg, v = 0 and the d (3)Πg, v = 6 states. Fifty seven rotational transitions in the P, Q, and R branches of all spin sub-states are measured and yield accurate molecular constants of the newly found upper level 1 (5)Πu. In addition, satellite transitions (ΔJ ≠ ΔN) are observed and allow an accurate determination of the spin-orbit constant. The results are compared with high-level ab initio computations at the multi-reference configuration interaction level of theory. The high-lying quintet state is found to be predissociative and displays a shallow potential that accommodates three vibrational levels only.

Test of time dilation using stored Li+ ions as clocks at relativistic speed.

We present the concluding result from an Ives-Stilwell-type time dilation experiment using 7Li+ ions confined at a velocity of β=v/c=0.338 in the storage ring ESR at Darmstadt. A Λ-type three-level system within the hyperfine structure of the 7Li+3S1 →3P2 line is driven by two laser beams aligned parallel and antiparallel relative to the ion beam. The lasers' Doppler shifted frequencies required for resonance are measured with an accuracy of <4×10(-9) using optical-optical double resonance spectroscopy. This allows us to verify the special relativity relation between the time dilation factor γ and the velocity β, γ√1-β2=1 to within ±2.3×10(-9) at this velocity. The result, which is singled out by a high boost velocity β, is also interpreted within Lorentz invariance violating test theories.

Spectroscopy and dynamics of the predissociated, quasi-linear S2 state of chlorocarbene

In this work, we report on the spectroscopy and dynamics of the quasi-linear S(2) state of chlorocarbene, CHCl, and its deuterated isotopologue using optical-optical double resonance (OODR) spectroscopy through selected rovibronic levels of the S(1) state. This study, which represents the first observation of the S(2) state in CHCl, builds upon our recent examination of the corresponding state in CHF, where pronounced mode specificity was observed in the dynamics, with predissociation rates larger for levels containing bending excitation. In the present work, a total of 14 S(2) state vibrational levels with angular momentum l = 1 were observed for CHCl, and 34 levels for CDCl. The range of l in this case was restricted by the pronounced Renner-Teller effect in the low-lying S(1) levels, which severely reduces the fluorescence lifetime for levels with K(a) > 0. Nonetheless, by exploiting different intermediate S(1) levels, we observed progressions involving all three fundamental vibrations. For levels with long predissociation lifetimes, rotational constants were determined by measuring spectra through different intermediate J levels of the S(1) state. Plots of the predissociation linewidth (lifetime) vs. energy for various S(2) levels show an abrupt onset, which lies near the calculated threshold for elimination to form C((3)P) + HCl on the triplet surface. Our experimental results are compared with a series of high level ab initio calculations, which included the use of a dynamically weighted full-valence CASSCF procedure, focusing maximum weight on the state of interest (the singlet and triplet states were computed separately). This was used as the reference for subsequent Davidson-corrected MRCI(+Q) calculations. These calculations reveal the presence of multiple conical intersections in the singlet manifold.

Testing Time Dilation on Fast Ion Beams

We report the status of an experimental test of time dilation in Special Relativity. This is accomplished by simultaneously measuring the forward and backward Doppler shifts of an electronic transition of fast moving ions, using high-precision laser spectroscopy. From these two Doppler shifts both the ion velocity β = v/c and the time dilation factor can be derived. From measurements based on saturation spectroscopy on lithium ions stored at β = 0.03 and β = 0.06 in the TSR heavy-ion storage ring, we achieved an upper limit for a \U0001d4aa[β2] deviation from Special Relativity of . In recent measurements on a β = 0.34 Li+ beam in the ESR storage ring we used optical-optical double-resonance spectroscopy which, in combination with the TSR result, gives improved sensitivity on the \U0001d4aa[β4] term of . We discuss current limitations and possible improvements that promise an enhancement of the sensitivity by at least one order of magnitude in the future.

Optical-optical double resonance spectroscopy of the quasi-linear S2 state of CHF and CDF. I. Spectroscopic analysis

In this work, we report on our full results of the spectroscopic analysis of the quasi-linear S(2) state of the prototypical halocarbene, CHF, and its deuterated isotopomer CDF using optical-optical double resonance spectroscopy through the S(1) state. A total of 51 S(2) state vibrational levels with angular momenta in the range [script-l] = 0-3 were observed for CHF, and 76 levels for CDF. Progressions involving all three fundamental vibrations were observed, and rotational constants were determined for each of these levels by measuring spectra through different intermediate J levels of the S(1) state. Our experimental results are in excellent agreement with the predictions of vibrational calculations using the discrete variable representation method. The variational vibrational calculations were performed with an analytic potential energy surface fit to ab initio data by the method of interpolating moving least squares. The ab initio data are Davidson-corrected multi-reference configuration interaction calculations based on a state-averaged multiconfigurational self-consistent field reference incorporating a generalized dynamic weighting scheme.

Optical-optical double resonance spectroscopy of the quasi-linear S2 state of CHF and CDF. II. Predissociation and mode-specific dynamics

In this work, we report on our full results of the dynamics of the quasi-linear, predissociated S(2) state of the prototypical halocarbene, CHF, and its deuterated isotopomer CDF using optical-optical double resonance spectroscopy through the S(1) state. Homogeneous linewidths were determined for a total of 51 S(2) state vibrational levels with angular momenta in the range [script-l] = 0-3 for CHF, and 76 levels for CDF. Progressions involving all three fundamental vibrations were observed. The linewidth data reveal pronounced mode specificity for both CHF and CDF, where pure bending states have the largest linewidths. For CDF, the linewidths are uniformly narrower. Calculated (CCSD(T)/aug-cc-pVQZ//MP2/aug-cc-pVQZ) stationary points on the CHF potential energy surface show that two dissociative pathways are available at the energies accessed in this experiment: dissociation on the triplet surface, over a barrier, to form C((3)P) + HF, and dissociation to ground state CF + H products. The former is excluded as a primary channel based on the small spin-orbit coupling in this system. A 27-state dynamically weighted full-valence complete active space self-consistent field calculation was performed with maximal weight focused on the S(2) state, which was then used as a reference for Davidson-corrected multireference configuration interaction calculations MRCI(+Q) of the three lowest A(') and two lowest A(") states. These calculations reveal the presence of multiple conical intersections in the singlet manifold. Consistent with our experimental results, the most important of these involves the repulsive S(3) state, which conically intersects with S(2) at linearity.

Preparatory measurements for a test of time dilation in the ESRThis paper was presented at the International Conference on Precision Physics of Simple Atomic Systems, held at École de Physique, les Houches, France, 30 May – 4 June, 2010.

We present preparatory measurements for an improved test of time dilation at the experimental storage ring (ESR) at GSI in Darmstadt. A unique combination of particle accelerator experiments and laser spectroscopy is used to perform this test with the highest precision. 7Li+ ions are accelerated to 34% of the speed of light at the GSI Helmholtzzentrum für Schwerionenforschung and stored in the experimental storage ring. The forward and backward Doppler shifts of an electric dipole transition of these ions are measured with laser spectroscopy techniques. From these Doppler shifts, both the ion velocity β = ν/c and the time dilation factor [Formula: see text] can be derived for testing Special Relativity. Two laser systems have been developed to drive the 3S1→3P2 transition in 7Li+. Moreover, a detector system composed of photomultipliers, both to monitor the exact laser ion beam overlap as well as to optimize fluorescence detection, has been set up and tested. We investigate optical-optical double-resonance spectroscopy on a closed Λ-type three-level system to overcome Doppler broadening. A residual, broadened fluorescence background caused by velocity-changing processes in the ion beam is identified, and a background subtraction scheme implemented. At the present stage the experimental sensitivity, although already comparable with previous measurements on slower ion beams at the TSR storage ring that led to [Formula: see text] &lt; 8.4 × 10–8, suffer from a poor signal-to-noise ratio. Modifications of the ion source as well as the detection system are discussed that promise to improve the sensitivity by one order of magnitude.

Spectroscopic observations, spin-orbit functions, and coupled-channel deperturbation analysis of data on theA Σ1u+andb Π3ustates ofRb2

We present experimentally derived potential curves and spin-orbit interaction functions for the strongly perturbed $A\text{ }{^{1}\ensuremath{\Sigma}}_{u}^{+}$ and $b\text{ }{^{3}\ensuremath{\Pi}}_{u}$ states of the rubidium dimer. The results are based on laser-induced fluorescence and optical-optical double-resonance polarization spectroscopy measurements combined with earlier laser-induced fluorescence data. We used an analytic potential (Hannover form) incorporated in a discrete variable representation of the Hamiltonian matrix for numerical energy-level calculation. A previous vibrational assignment of the $A$ levels is confirmed, and very probable vibrational assignment for the $b$ levels is also obtained. Currently, the rms residual of our fit is $0.053\text{ }{\text{cm}}^{\ensuremath{-}1}$ as compared to the typical experimental uncertainties that are estimated to be $0.005\text{ }{\text{cm}}^{\ensuremath{-}1}$. Fitted diagonal and off-diagonal spin-orbit functions are obtained and compared with ab initio calculations by all electrons and effective core pseudopotential methods. Analysis of the computational results yields an explanation for the ubiquitous single minima in these spin-orbit functions, which can be represented approximately by Morse-type functions.

Sub-Doppler laser spectroscopy on relativistic beams and tests of Lorentz invariance

We demonstrate sub-Doppler laser spectroscopy with a beam of ${^{7}\text{L}\text{i}}^{+}$ ions stored at 33.8% of the speed of light in the experimental storage ring at GSI. Using two lasers, the one copropagating and the other counterpropagating, with respect to the ion beam, a fluorescence line is observed via optical-optical double-resonance spectroscopy on a $\ensuremath{\Lambda}$-type level configuration. A linewidth of $\ensuremath{\approx}114\text{ }\text{MHz}$ is found, which is 12 times narrower than the Doppler broadening due to the momentum spread of the ion beam. Interpreted as a test of Lorentz invariance, we find $|{\stackrel{\ifmmode \hat{}\else \^{}\fi{}}{\ensuremath{\alpha}}}_{2}|l1.2\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}5}$, a $25\ifmmode\times\else\texttimes\fi{}$ tighter limit on $O\mathbf{(}{(v/c)}^{4}\mathbf{)}$ deviations from time dilation than any other experiment.

Observation of the nd Δ1g (n=6, 7, and 8) Rydberg states of Na2 by optical-optical double resonance spectroscopy: L uncoupling and perturbations

The nd (1)Delta(g) (n = 6, 7, and 8) Rydberg states of Na(2) correlating with the asymptotic limits of Na(3s) + Na(nd) have been observed using high-resolution cw optical-optical double resonance spectroscopy corresponding to the rovibrational transitions X (1)Sigma(g)(+)(v("),J(")) + h nu(pump) --> B (1)Pi(u)(v('),J(')) + h nu(probe) --> nd (1)Delta(g)(v,J). Totals of 104, 83, and 45 identified rovibrational e/f-parity levels in the ranges of v = 0-11, 11 < or = J < or = 83; v = 0-10, 11 < or = J < or = 83; and v = 0-10, 11 < or = J < or = 65, have been assigned to the 6d (1)Delta(g), 7d (1)Delta(g), and 8d (1)Delta(g) states, respectively. Using the observed quantum levels, molecular constants were determined from the Dunham fits of the e-parity levels and the Rydberg-Klein-Rees potential curves were constructed for the nd (1)Delta(g)(n = 6-8) states. The characteristics of the estimated Lambda-doubling splitting constants (q(0), q(v), and mu) with n(= 5-8) of the nd (1)Delta(g) series have been explored. Detailed investigations reveal that the nd (1)Delta(g)(n = 6-8) states involve L uncoupling from the internuclear axis and each of these states is affected by an asymmetric perturbation caused by the up and down adjacent states. The rotational-branch intensity and position anomalies in the observed spectra of the nd (1)Delta(g) series (n = 5-8) of Na(2) lead to the conclusion that due to the effects of the L-uncoupling perturbations, the same l complexes approaching the same ion-core limits result in the same l-mixing processes which lead to the formation of the supercomplexes due to the anisotropy of the molecular-ion [Na(2)(+)(3s)] field. This would open up opportunities to study the effects of L uncoupling and perturbations in the nd series and high Rydberg states of other alkali dimers.

Observation of the 7Πg State of Na2 by Optical−Optical Double Resonance Spectroscopy

The 71Pig Rydberg state of Na2 correlating with the separated atom limit Na(3s) + Na(5p) has been observed using high-resolution cw optical-optical double resonance spectroscopy. A total of 104 identified rovibrational levels in the range v = 0-12 and 11 </= J </= 44 have been assigned to the 71Pig state. Dunham coefficients were determined, and the Rydberg-Klein-Rees potential curve in the range of R = 2.99-4.66 A was derived for the 71Pig state using the observed quantum levels. The important molecular properties are the potential minimum Te = 36 633.00(23) cm-1 at Re = 3.6313(29) A, omegae = 115.75(13) cm-1, and Be = 0.111 22(17) cm-1. A detailed discussion of this investigation of the 71Pig state is provided.