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Physical Chemistry Chemical Physics

Spectroscopic analysis of the coupled 11Π, 23Σ+ (Ω = 0−, 1), and b3Π (Ω = 0±, 1, 2) states of the KRb molecule using both ultracold molecules and molecular beam experiments

Jin‐Tae Kim, Yonghoon Lee, Bongsoo Kim, Dajun Wang, William C. Stwalley, P. L. Gould, Edward E. Eyler

Published Jan 1, 2011• 18 citations
Publisher

Abstract

We report the spectroscopic characterization of excited electronic states of KRb by combining spectra from molecular beam (MB) experiments with those from ultracold molecules (UM) formed by photoassociation (PA) of ultracold atoms. Spectra involving the 1(1)Π, 2(3)Σ(+), and b(3)Π states in a strongly perturbed region have been identified. This approach provides a powerful method to identify the vibrational levels of the excited electronic states perturbed globally by neighboring electronic states. This is because the two sets of spectra from the UM and the MB experiments probe the same energy region from very different initial electronic states. The UM experiments utilize high v'' levels of the a(3)Σ(+) state with large internuclear separations, while the MB experiments utilize low v'' levels of the ground X(1)Σ(+) state with near-equilibrium internuclear separations. Only the Ω = 1 levels of the 2(3)Σ(+) and b(3)Π states are observed in the MB spectra, while the Ω = 0(-), 1 levels of the 2(3)Σ(+) state and the Ω = 0(±), 1, 2 levels of the b(3)Π state are observed in the UM spectra.

DOI
10.1039/c1cp21207a

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We report the spectroscopic characterization of excited electronic states of KRb by combining spectra from molecular beam (MB) experiments with those from ultracold molecules (UM) formed by photoassociation (PA) of ultracold atoms. Spectra involving the 1(1)Π, 2(3)Σ(+), and b(3)Π states in a strongly perturbed region have been identified. This approach provides a powerful method to identify the vibrational levels of the excited electronic states perturbed globally by neighboring electronic states. This is because the two sets of spectra from the UM and the MB experiments probe the same energy region from very different initial electronic states. The UM experiments utilize high v'' levels of the a(3)Σ(+) state with large internuclear separations, while the MB experiments utilize low v'' levels of the ground X(1)Σ(+) state with near-equilibrium internuclear separations. Only the Ω = 1 levels of the 2(3)Σ(+) and b(3)Π states are observed in the MB spectra, while the Ω = 0(-), 1 levels of the 2(3)Σ(+) state and the Ω = 0(±), 1, 2 levels of the b(3)Π state are observed in the UM spectra.
By using a combination of molecular beam (MB) excitation spectra and two distinct ultracold molecule excitation spectra (UM+ and UM-), we have assigned high vibrational levels of the A and 3 (1)Σ(+) states from absorption spectra of the mutually strongly perturbed A (1)Σ(+) - 3 (1)Σ(+) - 1 (1)Π - 2 (3)Σ(+) - b (3)Π states of ultracold (39)K(85)Rb molecules in the energy region between 15,116 and 16,225 cm(-1) above the minimum of the ground X (1)Σ(+) state. The ultracold molecules (UM+ and UM-) are formed by radiative decay following photoassociation (PA) to a specific level of the 3(0(+)) state (UM+) or to a specific level of the 3(0(-)) state (UM-). We observe that the A and 3 (1)Σ(+) states are observable in the UM+ spectra, but absent from the UM- spectra. This is explained by considering Hund's case (c) selection rules and transition dipole moments between the upper excited A (1)Σ(+) (2(0(+))) state and the three Ω components (0(+), 0(-), and 1) at the ground-state dissociation limit. We propose further investigations of the extended potential wells of the A and 3 (1)Σ(+) states by combining short-range MB excitation spectra in a narrow Franck-Condon (FC) window near R(e) of the X (1)Σ(+) state, and long-range UM (and PA) excitation spectra, which have much larger FC windows.
We have studied resonance-enhanced two-photon ionization of ultracold 39 K 85 Rb molecules in highly excited long-range vibrational levels of the X 1 Σ + and a 3 Σ + states. These molecules are formed by photoassociation (PA) of ultracold 39 K and 85 Rb atoms, followed by spontaneous emission to the X 1 Σ + and a 3 Σ + states. In the range 15 500–17 200 cm −1 , we observe many intermediate and long-range levels of the previously unobserved 4 3 Σ + and 4 1 Σ + states and evidence for the onset of the previously unobserved 3 3 Π state. The observed vibrational spectra of these states are in very good agreement with calculated vibrational levels based on the ab initio potentials of Rousseau, Allouche and Aubert-Frécon. Such experiments illustrate some of the unique advantages of using PA-produced ultracold molecules for investigation of long-range vibrational levels and long-range forces, and for unravelling dense spectra because only a few rotational levels are populated.
Convenient state-selective detection methods are proposed for exploring triplet Rydberg states from the metastable a 3 Σ + state of ultracold KRb molecules by resonance-enhanced two-photon ionization and time-of-flight (TOF) mass spectroscopy. This would allow the first accurate determination of the ionization potential. Particularly suitable resonant intermediate states include the 2 3 Π Ω , 3 3 Σ + and 4 3 Σ + states, and we report spectroscopic studies of these states. For the 2 3 Π Ω state, the spin–orbit components (Ω = 0 + , 0 − , 1 and 2) have been investigated and a shallow long-range state (5(0 + )) at ∼ 9.3 Å has been observed. We compare our observations of these three states with predictions based on ab initio potential energy curves. Such studies may also permit the direct observation of autoionizing resonances leading to efficient formation of low-lying rovibrational levels of the 2 Σ + ground state of KRb + , ideally in the v + = 0, N + = 0 level.
We report the observation and analysis of the 3 (3)ΠΩ double-minimum electronic excited state of (39)K(85)Rb. The spin-orbit components (0(+), 0(-), 1, and 2) of this state are investigated based on potentials developed from the available ab initio potential curves. We have assigned the vibrational levels v' = 2-11 of the 3 (3)Π1,2 potentials and v' = 2-12 of the 3(3)Π0(+/-) potential. We compare our experimental observations of the 3 (3)ΠΩ state with predictions based on theoretical potentials. The observations are based on resonance enhanced multiphoton ionization of ultracold KRb in vibrational levels v" = 14-25 of the a (3)Σ(+) state. These a-state ultracold molecules are formed by photoassociation of ultracold (39)K and (85)Rb atoms to the 5(1) state of KRb followed by spontaneous emission to the a state.
We present spectroscopic studies of ultracold LiRb molecules using ionization detection. The molecules are created by cooling and trapping Li and Rb atoms in overlapping magneto-optical traps (MOTs) and using light resonant with a free-bound transition to create weakly bound excited state molecules in a process known as photoassociation (PA). We explore weakly bound vibrational levels of LiRb with PA spectroscopy using ionization detection and, where possible, compare our results with earlier measurements performed in our lab using trap-loss spectroscopy. In addition, we also probe vibrational levels of the ground triplet electronic state and excited electronic states using resonantly enhanced multiphoton ionization (REMPI) spectroscopy. We identify several vibrational levels of the α3Σ+, (3)3ΠΩ and (4)3Σ + states and compare our observations with theoretical calculations. As LiRb is one of the least studied heteronuclear diatomic molecules, these studies are aimed towards exploring the molecular structure. The spectroscopic work is also in line with the long-term project goals of transferring ultracold LiRb molecules into the lowest rotational and vibrational levels of the ground singlet electronic state. Molecules in this rovibronic ground state possess a large electric dipole moment, which is essential for application of ultracold molecules in various quantum computation schemes. The rovibronic ground state will also be an ideal starting point for investigating molecular entangled states.
This thesis describes the spectroscopy work on ultracold 39K 85Rb molecules as part of our effort towards producing ground-state ultracold polar molecules. ^ The starting points of our experiment are laser cooled and trapped K and Rb atoms in dual-species MOTs and the molecule formation method is photoassociation (PA). A fraction of the PA-produced excited-state molecules can spontaneously emit to the two lowest electronic states, the X 1Σ + state and the a 3Σ + state, to form high vibrational level molecules. In order to develop a population transfer scheme to make deeply bound molecules, we have studied the spectroscopy of KRb in several steps. Besides the PA step, we have also carried out a state-selective detection experiment to study the population distribution of the high vibrational level molecules formed via spontaneous emission. The detection method is pulsed-laser based ion time-of-flight mass spectroscopy. Due to the linewidth limitations of the pulsed laser, this detection method can only resolve vibrational structures. A cw laser induced ion depletion spectroscopy technique has been developed in order to obtain rotational resolution. Using this ion depletion method, we have studied a possible stimulated Raman transfer scheme via the 3 1Σ+ state. To this end, we have obtained all the spectroscopic information required to produce deeply bound KRb molecules in a single vibrational and rotational level. ^ Several other spectroscopic studies using the high vibrational level ultracold molecules are also discussed. ^