We describe a method for determining the radiative decay properties of a molecule by studying the saturation of laser-induced fluorescence and the associated power broadening of spectral lines. The fluorescence saturates because the molecules decay to states that are not resonant with the laser. The amplitudes and widths of two hyperfine components of a spectral line are measured over a range of laser intensities and the results compared to a model of the laser-molecule interaction. Using this method we measure the lifetime of the A(v'=0) state of CaF to be tau=19.2 \pm 0.7 ns, and the Franck-Condon factor for the transition to the X(v=0) state to be Z=0.987 (+0.013 || -0.019). In addition, our analysis provides a measure of the hyperfine interval in the lowest-lying state of A(v'=0), Delta_e=4.8 \pm 1.1 MHz.
We present quantitative measurements of the photoassociation of cesium molecules inside a far-detuned optical dipole trap. A model of the trap depletion dynamics is derived which allows to extract absolute photoassociation rate coefficients for the initial single-photon photoassociation step from measured trap-loss spectra. The sensitivity of this approach is demonstrated by measuring the Franck-Condon modulation of the weak photoassociation transitions into the low vibrational levels of the outer well of the 0g- state that correlates to the 6s+6p3/2 asymptote. The measurements are compared to…
The fluorescence spectrum resulting from laser excitation of the A^{2}Π_{1/2} - X^{2}Σ^{+} (0,0) band of ytterbium monofluoride, YbF, has been recorded and analyzed to determine the Franck-Condon factors. The measured values are compared with those predicted from Rydberg-Klein-Rees (RKR) potential energy curves. From the fluorescence decay curve the radiative lifetime of the A^{2}Π_{1/2} state is measured to be 28\pm2 ns, and the corresponding transition dipole moment is 4.39\pm0.16 D. The implications for laser cooling YbF are discussed.
We present a method of transferring a cold atom between spatially separated microtraps by means of a Raman transition between the ground motional states of the two traps. The intermediate states for the Raman transition are the vibrational levels of a third microtrap, and we determine the experimental conditions for which the overlap of the wave functions leads to an efficient transfer. There is a close analogy with the Franck-Condon principle in the spectroscopy of molecules. Spin-dependent manipulation of neutral atoms in microtraps has important applications in quantum information processin…
Laser induced electronic excitations that spontaneously emit photons and decay directly to the initial ground state ("optical cycling transitions") are used in quantum information and precision measurement for state initialization and readout. To extend this primarily atomic technique to organic compounds, we theoretically investigate optical cycling of alkaline earth phenoxides and their functionalized derivatives. We find that optical cycle leakage due to wavefunction mismatch is low in these species, and can be further suppressed by using chemical substitution to boost the electron withdraw…
We propose how to explore the Franck-Condon (FC) physics via a single ion confined in a spin-dependent potential, formed by the combination of a Paul trap and a magnetic field gradient. The correlation between electronic and vibrational degrees of freedom, called as electron-vibron coupling, is induced by a nonzero gradient. For a sufficiently strong electron-vibron coupling, the FC blockade of low-lying vibronic transitions takes place. We analyze the feasibility of observing the FC physics in a single trapped ion, and demonstrate various potential applications of the ionic FC physics in quan…
Ultracold photoassociation is typically performed at large internuclear separations, where the scattering wavefunction amplitude is large and Franck-Condon overlap is maximized. Recently, work by this group and others on alkali-metal diatomics has shown that photoassociation can efficiently form molecules at short internuclear distance in both homonuclear and heteronuclear dimers. We propose that this short-range photoassociation is due to excitation near the wavefunction amplitude maximum at the inner wall of the lowest triplet potential. We show that Franck-Condon factors from the highest-en…
We propose and experimentally investigate a scheme for narrow-line cooling of KRb molecules in the rovibrational ground state. We show that the spin-forbidden $\mathrm{X^1Σ^+} \rightarrow \mathrm{b^3Π_{0^+}}$ transition of KRb is ideal for realizing narrow-line laser cooling of molecules because it has highly diagonal Franck-Condon factors and narrow linewidth. In order to confirm the prediction, we performed the optical and microwave spectroscopy of ultracold $^{41}$K$^{87}$Rb molecules, and determined the linewidth ($2π\times$ 4.9(4) kHz) and Franck-Condon factors for the $\mathrm{X^1Σ^+} (v…
An optical cycling center (OCC) is a recently coined term to indicate two electronic states within a complex quantum object that can repeatedly experience optical laser excitation and spontaneous decay, while being well isolated from its environment. Here we present a quantitative understanding of electronic, vibrational, and rotational excitations of the polyatomic SrOH molecule, which possesses a localized OCC near its Sr atom. In particular, we describe the vibrationally-dependent trends in the Franck-Condon factors of the bending and stretching modes of the molecular electronic states coup…
The properties of photoassociation (PA) spectra near the intercombination line (the weak transition between $^{1}S_{0}$ and $^{3}P_{1}$ states) of group II atoms are theoretically investigated. As an example we have carried out a calculation for Calcium atoms colliding at ultra low temperatures of 1 mK, 1 $μ$K, and 1 nK. Unlike in most current photoassociation spectroscopy the Doppler effect can significantly affect the shape of the investigated lines. Spectra are obtained using Ca--Ca and Ca--Ca$^*$ short-range {\it ab initio} potentials and long-range van der Waals and resonance dipole poten…
We propose and demonstrate a novel technique that combines Raman scattering and optical cycling in molecules with diagonal Franck-Condon factors. This resonance Raman optical cycling manipulates molecules to behave like efficient fluorophores with discrete absorption and emission profiles that are readily separated for sensitive fluorescence detection in high background light environments. Using a molecular beam of our test species, SrF, we realize up to an average of $\approx20$ spontaneously emitted photons per molecule, limited by the interaction time, while using a bandpass filter to suppr…
We describe a simple experimental apparatus for laser ablation of barium monohydride (BaH) molecules and the study of their rovibrational spectra that are relevant to direct laser cooling. We present a detailed analysis of the properties of ablation plumes that can improve the understanding of surface ablation and deposition technologies. A range of absorption spectroscopy and collisional thermalization regimes has been studied. We directly measured the Franck-Condon factor of the $\mathrm{B}^2Σ^+(v'=0)\leftarrow\mathrm{X}^2Σ^+(v"=1)$ transition. Prospects for production of a high luminosity c…
A model based on the strong-field and Born-Oppenheimer approximations qualitatively describes the distribution over vibrational states formed in a diatomic molecular ion following ionization of the neutral molecule by intense laser pulses. Good agreement is found with a recent experiment [X. Urbain et al., Phys. Rev. Lett. 92, 163004 (2004)]. In particular, the observed deviation from a Franck-Condon-like distribution is reproduced. Additionally, we demonstrate control of the vibrational distribution by a variation of the peak intensity or a change of frequency of the laser pulse.
For laser cooling considerations, we have theoretically investigated the electronic, rovibrational and hypefine structures of BaF molecule. The highly diagonal Franck-Condon factors and the branching ratios for all possible transitions within the lowest-lying four electronic states have also been calculated. Meanwhile, the mixing between metastable A'2Δ and A2Π states and further the lifetime of the Δ state have been estimated since the loss procedure via Δ state would like fatally destroy the main quasi-cycling Σ-Π transition for cooling and trapping. The resultant hyperfine splittings of eac…
We report on the state-selective detection of near-dissociation ultracold KRb molecules in the ground $X^1Σ^+$ state and the metastable $a^3Σ^+$ state. The molecules are produced by photoassociation of ultracold atoms followed by radiative decay into high vibrational levels of the $X$ and $a$ states. Detection utilizes resonance-enhanced one-color two-photon ionization, followed by time-of-flight mass spectroscopy. Scanning the detection laser frequency over the range 582-625 nm, we observe transitions from the $v''$=86-92 levels of the $X$ state, which are bound by up to 30 cm$^{-1}$, and the…
We theoretically study saturation effects induced by an external static electric field on photoassociation (PA) of a heteronuclear atom pair. A static electric field influences scattering wave-function of two heteronuclear atoms as described in [D. Chakraborty, J. Hazra and B. Deb, J. Phys. B. {\bf 44} 095201 (2011)]. For certain values of electric field strengths there exist anisotropic resonances in ground state scattering leading to a large modification of scattering wave-function at short and intermediate separations where photoassociative Franck-Condon overlap is significant. Photoassocia…
We demonstrate a scheme for optical cycling in the polar, diatomic molecule strontium monofluoride (SrF) using the $X ^2Σ^+\toA^2Π_{1/2}$ electronic transition. SrF's highly diagonal Franck-Condon factors suppress vibrational branching. We eliminate rotational branching by employing a quasi-cycling $N=1\to N^\prime=0$ type transition in conjunction with magnetic field remixing of dark Zeeman sublevels. We observe cycling fluorescence and deflection through radiative force of an SrF molecular beam using this scheme. With straightforward improvements our scheme promises to allow more than $10^5$…
Laser cooling of molecules employing broadband optical pumping involves a timescale separation between laser excitation and spontaneous emission. Here, we optimize the optical pumping step using shaped laser pulses. We derive two optimization functionals to drive population into those excited state levels that have the largest spontaneous emission rates to the target state. We show that, when using optimal control, laser cooling of molecules works even if the Franck-Condon map governing the transitions is preferential to heating rather than cooling. Our optimization functional is also applicab…
We measure the upper state lifetime and two ratios of vibrational branching fractions f_{v'v} on the B^{3}Π_{1}(v') - X^{1}Σ^{+}(v) transition of TlF. We find the B state lifetime to be 99(9) ns. We also determine that the off-diagonal vibrational decays are highly suppressed: f_{01}/f_{00} < 2x10^{-4} and f_{02}/f_{00} = 1.10(6)%, in excellent agreement with their predicted values of f_{01}/f_{00} < 8x10^{-4} and f_{02}/f_{00} = 1.0(2)% based on Franck-Condon factors calculated using Morse and RKR potentials. The implications of these results for the possible laser cooling of TlF and fundamen…
A rational approach to identify polyatomic molecules that appear to be promising candidates for direct Doppler cooling with lasers is outlined. First-principle calculations for equilibrium structures and Franck--Condon factors of selected representatives with different point-group symmetries (including chiral non-symmetric group C$_1$) have been performed and high potential for laser-cooling of these molecules is indicated.
Starting from an ultracold sample of ground-state $^{23}$Na$^{87}$Rb molecules, we investigate the lowest ro-vibrational level of the $b^3Π$ state with high resolution laser spectroscopy. This electronic spin-forbidden $X^1Σ^+ \leftrightarrow b^3Π$ transition features a nearly diagonal Franck-Condon factor and has been proposed useful for probing and manipulating the ultracold molecular gas. We measure the transition strength directly by probing the ac Stark shift induced by near resonance light and determine the total excited-state spontaneous emission rate by observing the loss of molecules.…
Alkaline earth monoalkoxide free radicals (MORs) have molecular properties conducive to direct laser cooling to sub-millikelvin temperatures. Using dispersed laser induced fluorescence (DLIF) measurements from a pulsed supersonic molecular beam source we determine vibrational branching ratios and Franck-Condon factors for the MORs CaOH and CaOCH$_{3}$. With narrow linewidth continuous-wave dye laser excitation, we precisely measure fluorescence branching for both $\tilde{X}-\tilde{A}$ and $\tilde{X}-\tilde{B}$ electronic systems in each molecule. Weak symmetry-forbidden decays to excited bendi…
The NL-eEDM collaboration is building an experimental setup to search for the permanent electric dipole moment of the electron in a slow beam of cold barium fluoride molecules [Eur. Phys. J. D, 72, 197 (2018)]. Knowledge of molecular properties of BaF is thus needed to plan the measurements and in particular to determine an optimal laser-cooling scheme. Accurate and reliable theoretical predictions of these properties require incorporation of both high-order correlation and relativistic effects in the calculations. In this work theoretical investigations of the ground and the lowest excited st…
Optical molecular clocks promise unparalleled sensitivity to the temporal variation of the electron-to-proton mass ratio and insight into possible new physics beyond the Standard Model. We propose to realize a molecular clock with bosonic $^{174}$Yb$_2$ molecules, where the forbidden $^1$S$_0$$\rightarrow$$^3$P$_0$ clock transition would be induced magnetically. The use of a bosonic species avoids possible complications due to hyperfine structure present in fermionic species. While direct clock line photoassociation would be challenging, weakly bound ground state molecules could be produced by…
