Structural and Spectroscopic Study of the LiRb Molecule beyond the Born–Oppenheimer Approximation

Jendoubi, Imen; Berriche, H.; Ouada, H. Ben; Gadéa, Florent Xavier

doi:10.1021/jp209106w

Cited by 20 publications

(30 citation statements)

References 75 publications

(168 reference statements)

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“…29 cm −1 and better than all other reported theoretical values 23,25,27,28,33. The ω e is very close to the experimental value 19534 cm −1 as well as the theoretical values 195.3, 23 195.18, 26 194.0, 25 195.0, 24 196.02, 27 194.0, 33 and 196.2 28 cm −1 .…”

supporting

confidence: 82%

Ab initio studies on the spin-forbidden cooling transitions of the LiRb molecule

You

Yang

Zhang

et al. 2016

Phys. Chem. Chem. Phys.

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The spin-forbidden cooling of the LiRb molecule is investigated based on ab initio quantum chemistry calculations. The multireference configuration interaction method is used to generate the potential energy curves (PECs) of the ground state X(1)Σ(+) and the low-lying excited states a(3)Σ(+), B(1)Π, and b(3)Π. The spin-orbit coupling effects for the PECs and the transition dipole moments (TDMs) between the X(1)Σ(+), b(3)Π and a(3)Σ(+) states are also calculated. The analytical functions for the PECs are deduced. The rovibrational energy levels, the spectroscopic parameters and the Franck-Condon factors (FCF) are determined by solving the Schrödinger equation of nuclear movement with the obtained analytical functions. The b(3)Π0 ↔ X(1)Σ(+) and b(3)Π1 ↔ X(1)Σ(+) transitions have highly diagonal distributed FCFs and non-zero TDMs, demonstrating that the LiRb molecule could be a very promising candidate for laser cooling. Therefore, a three-cycle laser cooling scheme for the molecule has been proposed based on these two spin-forbidden transitions. Using the radiative lifetime and linewidth calculated from the obtained TDM functions, we present further analysis of the cooling of LiRb and the corresponding KRb molecule. The transition b(3)Π0 ↔ X(1)Σ(+) is found to be a practical transition to cool the LiRb molecule, and a sub-microkelvin cool temperature could be reached for the KRb molecule using a similar laser cooling scheme.

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supporting

confidence: 82%

Ab initio studies on the spin-forbidden cooling transitions of the LiRb molecule

You

Yang

Zhang

et al. 2016

Phys. Chem. Chem. Phys.

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“…In this section, we demonstrate our TDM extraction procedure using time-resolved fluorescence for an excited lithium-rubidium dimer (LiRb) wave packet evolving on the spin orbit (SO) coupled A 1 ⌺ u ϩ and b 3 ⌸ electronic states. 28,29,30,31 In Fig. 1a, we depict the ground state singlet X 1 ⌺ g ϩ and triplet a 3 ⌺ + and two lowest excited PES of LiRb.…”

Section: Results: Lirbmentioning

confidence: 99%

Using coherent control to extract the phases of electronic transition-dipole matrices: the LiRb case

Menzel-JonesCian

ShapiroMoshe

2014

Can. J. Chem.

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We show that "bichromatic coherent control" (BCC) enables the determination of the amplitudes (= magnitudes + phases) of individual transition-dipole matrix elements (TDMs) and the amplitude of time-evolving wave packets from timeresolved fluorescence data. In the present use of BCC, one induces quantum interferences using two external laser fields to coherently deplete the population of different pairs of excited energy eigenstates. The BCC-induced depletion is supplemented by the computation of the Fourier integral of the time-resolved fluorescence at the beat frequencies of the two states involved. The combination of BCC and Fourier transform enables the determination of both the expansion coefficients of the wave packet in a basis of vibrational energy eigenstates and the amplitudes of the ͗ f Խ Խ s ͘ electronic TDMs linking the excited and ground rovibrational states. We illustrate our method by determining the amplitudes of the TDMs linking the vibrational states of the A 1 ⌺ u ϩ ϳ b 3 ⌸ spin orbit coupled potentials to both the singlet X 1 ⌺ u ϩ and the triplet a 3 ⌺ u ϩ electronic ground states in LiRb. The approach, which is found to be quite robust against errors in the BCC procedure and experimental data, can be readily generalized to the imaging of wave packets of polyatomic molecules.Résumé : Nous montrons que le « contrôle cohérent bichromatique » (CCB) permet de déterminer les amplitudes (= grandeurs + phases) des éléments de matrice de transition dipolaire (EMTD) individuels et l'amplitude des paquets d'ondes à évolution temporelle au moyen de données de fluorescence résolues en temps. La présente utilisation du CCB consiste à induire des interférences quantiques en se servant de deux champs laser externes en vue de réduire de manière cohérente la population de différentes paires d'états propres excités d'énergie. La réduction induite par le CCB est complétée par le calcul de l'intégrale de Fourier de la fluorescence résolue en temps aux fréquences de battement des deux états concernés. La combinaison du CCB et de la transformée de Fourier permet de déterminer les coefficients d'expansion du paquet d'ondes dans une base d'états propres d'énergie de vibration, ainsi que les amplitudes des EMTD électroniques ͗ f Խ Խ s ͘ reliant les états rovibrationnels excités et fondamentaux. Pour illustrer notre méthode, nous déterminons les amplitudes des EMTD reliant les états vibrationnels des potentiels avec couplage spin orbite A 1 ⌺ u ϩ ϳ b 3 ⌸ aux états électroniques fondamentaux singulet X 1 ⌺ u ϩ ainsi que triplet a 3 ⌺ u ϩ dansLiRb. L'approche, qui s'avère assez robuste aux erreurs dans la procédure de CCB et les données expérimentales, est facilement généralisable à l'imagerie des paquets d'ondes de molécules polyatomiques. [Traduit par la Rédaction]

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“…Several theoretical studies of the electronic structure of alkali dimers have been interested in studying the heteronuclear alkali dimers using various quantum chemistry methods to determine the potential energy curves of the ground and exited states of RbCs, NaRb, and LiRb, NaCs, LiCs, and CsK, KRb, LiK, NaK, and LiNa . Several theoretical studies have been performed for the LiRb molecule. The first theoretical study of the LiRb molecule was made by Korek et al based on pseudopotential and configuration interaction (CI) calculations.…”

Section: Introductionmentioning

confidence: 99%

“…Core‐valence correlation effects are quite important. Here, we used the well established core polarization potential (CPP) operator approach proposed by Muller et al In a very recent publication, similar methods were also used. However, we have here extended the study to a few additional states for each symmetry.…”

Section: Introductionmentioning

confidence: 99%

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Ab Initio Diabatic energies and dipole moments of the electronic states of RbLi molecule

et al. 2013

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For all states dissociating below the ionic limit Li(-) Rb(+) , we perform a diabatic study for (1) Σ(+) electronic states dissociating into Rb (5s, 5p, 4d, 6s, 6p, 5d, 7s, 4f) + Li (2s, 2p, 3s). Furthermore, we present the diabatic results for the 1-11 (3) σ, 1-8 (1,3) Π, and 1-4 (1,3) Δ states. The present calculations on the RbLi molecule are complementary to previous theoretical work on this system, including recently observed electronic states that had not been calculated previously. The calculations rely on ab-initio pseudopotential, core polarization potential operators for the core-valence correlation and full valence configuration interaction approaches, combined to an efficient diabatization procedure. For the low-lying states, diabatic potentials and permanent dipole moments are analyzed, revealing the strong imprint of the ionic state in the (1) Σ(+) adiabatic states. The transition dipole moment is used to evaluate the radiative lifetimes of the vibrational levels trapped in the 2 (1) Σ(+) excited states for the first time. In addition to the bound-bound contribution, the bound-free term has been evaluated using the Franck-Condon approximation and also exactly added to the total radiative lifetime.

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Structural and Spectroscopic Study of the LiRb Molecule beyond the Born–Oppenheimer Approximation

Cited by 20 publications

References 75 publications

Ab initio studies on the spin-forbidden cooling transitions of the LiRb molecule

Ab initio studies on the spin-forbidden cooling transitions of the LiRb molecule

Using coherent control to extract the phases of electronic transition-dipole matrices: the LiRb case

Ab Initio Diabatic energies and dipole moments of the electronic states of RbLi molecule

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