© 2026 Aqora Quantum S.A.S.

Terms Privacy Legal Notice

arXiv:1602.07753 · Journal of Physics B Atomic Molecular and Optical Physics

Short-range photoassociation from the inner wall of the lowest triplet potential of 85 Rb 2

R A Carollo, J L Carini, E E Eyler, P. L. Gould, W C Stwalley

Published Sep 19, 2016• 8 citations

Abstract

Abstract 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 (FCFs) from the highest-energy bound state can almost precisely reproduce FCFs from a low-energy scattering state, and that both calculations match experimental data from the near-zero positive-energy scattering state with reasonable accuracy. We also show that the corresponding photoassociation from the inner wall of the ground-state singlet potential at much shorter internuclear distance is weaker and undetectable under our current experimental conditions. We predict from FCFs that the strongest of these weaker short-range photoassociation transitions are one order of magnitude below our current sensitivity.

DOI: 10.1088/0953-4075/49/19/194001

Related papers

Ultracold photoassociative spectroscopy of heteronuclear alkali-metal diatomic molecules

He Wang, William C. Stwalley

We have examined and identified the excited long-range Hund’s case (c) molecular states of the ten heteronuclear alkali metal diatomic molecules which support bound states and can be probed by ultracold photoassociative spectroscopy. Analytical expressions for the heteronuclear long-range free-bound Franck–Condon factors as a function of the internuclear distance R and the vibrational quantum number v are derived and discussed. The KRb system has considerably stronger excited long-range interactions than any other heteronuclear alkali diatomic molecule and has very favorable Franck–Condon factors for the photoassociation process. The heteronuclear photoassociative spectroscopy will provide spectroscopic measurements of the binary elastic scattering lengths of heteronuclear cold collisions which are the crucial parameters for sympathetic cooling of mixed atomic gases.

The Journal of Chemical Physics•Apr 8, 1998•123 citations

Formation of ultracold metastable RbCs molecules by short-range photoassociation

C. Gabbanini, Olivier Dulieu

Ultracold metastable RbCs molecules are observed in a double species magneto-optical trap through photoassociation near the Rb(5S(1/2)) + Cs(6P(3/2)) dissociation limit followed by radiative stabilization. The molecules are formed in their lowest triplet electronic state and are detected by resonance enhanced two-photon ionization through the previously unobserved (3)(3)Π ← a (3)Σ(+) band. The large rotational structure of the observed photoassociation lines is assigned to the lowest vibrational levels of the 0(+) or 0(-) excited states correlated to the Rb(5P(1/2)) + Cs(6S(1/2)) dissociation limit. This demonstrates the possibility of inducing direct photoassociation in heteronuclear alkali-metal molecules at a short internuclear distance, as pointed out earlier [J. Deiglmayr et al., Phys. Rev. Lett., 2008, 101, 13304].

arXiv:1107.0547•Physical Chemistry Chemical Physics•Jan 1, 2011•47 citations

Theoretical Study of Photoassociation of Alkali-Metal Dimers

Junxia Cheng, Jia Wang, Zhenkun Tan +1 more

The photoassociation of alkali metal molecules (Rb2, Cs2, and RbCs) at short range is investigated in theory. Based on ab initio calculations to rationalize Franck–Condon filtering, the target states of photoassociation have been obtained. They correspond to vibrational transition levels from excited state (Rb2: $${v}{\kern 1pt} '$$ = 17–21, Cs2: $${v}{\kern 1pt} '$$ = 21–25, and RbCs: $${v}{\kern 1pt} '$$ = 18–22) to ground state. By using quantum wave-packet dynamic methods, the yields with time evaluation of the selected states are calculated interacting with a resonant laser pulse. Using gaussian pulse leads to the yield of Rb2 up to 82% at 860 fs. After a laser pulse, the positive chirp promotes the yield of vibrational states to increase, but the negative chirp inhibits it. That is to say, by changing the laser parameters and pulse shapes, it is much easier to control the photochemical process along desired direction. For photoassociation of alkali-metal dimers, homonuclear molecules have a better response to laser pulse than heteronuclear molecules. The efficiency of photochemical reaction of homonuclear molecules is much better and the photoassociative yield is much higher. Those conditions will provide an important reference and suggest a scheme for a feasible photoassociation for further experimental and theoretical research.

Russian Journal of Physical Chemistry A•Dec 1, 2021•1 citation

Formation of ultracold RbCs molecules by photoassociation

Nadia Bouloufa-Maafa, M Aymar, Olivier Dulieu +1 more

The formation of ultracold metastable RbCs molecules is observed in a double species magneto-optical trap through photoassociation below the 85 Rb(5S 1/2 ) + 133 Cs(6P 3/2 ) dissociation limit followed by spontaneous emission. The molecules are detected by resonance enhanced two-photon ionization. Using accurate quantum chemistry calculations of the potential energy curves and transition dipole moment, we interpret the observed photoassociation process as occurring at short internuclear distance, in contrast with most previous cold atom photoassociation studies. The vibrational levels excited by photoassociation belong to the 5th 0 + or the 4th 0 − electronic states correlated to the Rb(5P 1/2, 3/2 ) + Cs(6S 1/2 ) dissociation limit. The computed vibrational distribution of the produced molecules shows that they are stabilized in deeply bound vibrational states of the lowest triplet state. We also predict that a noticeable fraction of molecules is produced in the lowest level of the electronic ground state.

arXiv:1111.3503•Laser Physics•Sep 3, 2012•23 citations

Short-Range Photoassociation and Trilobite-Like States of Ultracold Rb2

Michael Bellos

I demonstrate the formation of rubidium dimers via photoassociation and spontaneous emission at short internuclear distances. This short-range photoassociation allows the formation of deeply bound molecules, including, for instance, the lowest rovibrational level of the lowest triplet state: a(0,0). This particular state is interesting because it is metastable against radiative decay, and possibly long-lived in optical and/or magnetic traps. In a second experiment, I demonstrate the population of trilobite-like excited states of Rb2. Trilobite-like states are bound by an unusual chemical bond, and can have large physical dimensions and electric dipole moments. I demonstrate the population of these states through the ultraviolet excitation of weakly bound molecules. By using the same ultraviolet excitation scheme, I place a new upper-bound on the minimum energy required to ionize 85Rb2 molecules.

•Jan 1, 2013•1 citation

Photoassociation spectrum of ultracold Rb atoms

Joseph D. Miller, Robert A. Cline, Daniel J. Heinzen

We study the photoassociative collisional loss of laser-cooled Rb atoms from a far-off resonance optical dipole force atom trap. We obtain a well-resolved photoassociation spectrum from 50 ${\mathrm{cm}}^{\mathrm{\ensuremath{-}}1}$ to 980 ${\mathrm{cm}}^{\mathrm{\ensuremath{-}}1}$ below the first excited dissociation limit of the ${\mathrm{Rb}}_{2}$ molecule. Two vibrational series associated with excited ${\mathrm{Rb}}_{2}$ $^{3}\mathrm{\ensuremath{\Sigma}}_{\mathit{g}}^{+}$ states are clearly visible. Oscillations in the associated Franck-Condon factors reflect the structure of the triplet ground state wave function. Our results clearly demonstrate the potential of photoassociation spectroscopy as a new probe of molecular structure.

Physical Review Letters•Oct 4, 1993•240 citations

Abstract 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 (FCFs) from the highest-energy bound state can almost precisely reproduce FCFs from a low-energy scattering state, and that both calculations match experimental data from the near-zero positive-energy scattering state with reasonable accuracy. We also show that the corresponding photoassociation from the inner wall of the ground-state singlet potential at much shorter internuclear distance is weaker and undetectable under our current experimental conditions. We predict from FCFs that the strongest of these weaker short-range photoassociation transitions are one order of magnitude below our current sensitivity.

We have examined and identified the excited long-range Hund’s case (c) molecular states of the ten heteronuclear alkali metal diatomic molecules which support bound states and can be probed by ultracold photoassociative spectroscopy. Analytical expressions for the heteronuclear long-range free-bound Franck–Condon factors as a function of the internuclear distance R and the vibrational quantum number v are derived and discussed. The KRb system has considerably stronger excited long-range interactions than any other heteronuclear alkali diatomic molecule and has very favorable Franck–Condon factors for the photoassociation process. The heteronuclear photoassociative spectroscopy will provide spectroscopic measurements of the binary elastic scattering lengths of heteronuclear cold collisions which are the crucial parameters for sympathetic cooling of mixed atomic gases.

Ultracold metastable RbCs molecules are observed in a double species magneto-optical trap through photoassociation near the Rb(5S(1/2)) + Cs(6P(3/2)) dissociation limit followed by radiative stabilization. The molecules are formed in their lowest triplet electronic state and are detected by resonance enhanced two-photon ionization through the previously unobserved (3)(3)Π ← a (3)Σ(+) band. The large rotational structure of the observed photoassociation lines is assigned to the lowest vibrational levels of the 0(+) or 0(-) excited states correlated to the Rb(5P(1/2)) + Cs(6S(1/2)) dissociation limit. This demonstrates the possibility of inducing direct photoassociation in heteronuclear alkali-metal molecules at a short internuclear distance, as pointed out earlier [J. Deiglmayr et al., Phys. Rev. Lett., 2008, 101, 13304].

The photoassociation of alkali metal molecules (Rb2, Cs2, and RbCs) at short range is investigated in theory. Based on ab initio calculations to rationalize Franck–Condon filtering, the target states of photoassociation have been obtained. They correspond to vibrational transition levels from excited state (Rb2:

{v}{\kern 1pt} '

= 17–21, Cs2:

{v}{\kern 1pt} '

= 21–25, and RbCs:

{v}{\kern 1pt} '

= 18–22) to ground state. By using quantum wave-packet dynamic methods, the yields with time evaluation of the selected states are calculated interacting with a resonant laser pulse. Using gaussian pulse leads to the yield of Rb2 up to 82% at 860 fs. After a laser pulse, the positive chirp promotes the yield of vibrational states to increase, but the negative chirp inhibits it. That is to say, by changing the laser parameters and pulse shapes, it is much easier to control the photochemical process along desired direction. For photoassociation of alkali-metal dimers, homonuclear molecules have a better response to laser pulse than heteronuclear molecules. The efficiency of photochemical reaction of homonuclear molecules is much better and the photoassociative yield is much higher. Those conditions will provide an important reference and suggest a scheme for a feasible photoassociation for further experimental and theoretical research.

The formation of ultracold metastable RbCs molecules is observed in a double species magneto-optical trap through photoassociation below the 85 Rb(5S 1/2 ) + 133 Cs(6P 3/2 ) dissociation limit followed by spontaneous emission. The molecules are detected by resonance enhanced two-photon ionization. Using accurate quantum chemistry calculations of the potential energy curves and transition dipole moment, we interpret the observed photoassociation process as occurring at short internuclear distance, in contrast with most previous cold atom photoassociation studies. The vibrational levels excited by photoassociation belong to the 5th 0 + or the 4th 0 − electronic states correlated to the Rb(5P 1/2, 3/2 ) + Cs(6S 1/2 ) dissociation limit. The computed vibrational distribution of the produced molecules shows that they are stabilized in deeply bound vibrational states of the lowest triplet state. We also predict that a noticeable fraction of molecules is produced in the lowest level of the electronic ground state.

I demonstrate the formation of rubidium dimers via photoassociation and spontaneous emission at short internuclear distances. This short-range photoassociation allows the formation of deeply bound molecules, including, for instance, the lowest rovibrational level of the lowest triplet state: a(0,0). This particular state is interesting because it is metastable against radiative decay, and possibly long-lived in optical and/or magnetic traps. In a second experiment, I demonstrate the population of trilobite-like excited states of Rb2. Trilobite-like states are bound by an unusual chemical bond, and can have large physical dimensions and electric dipole moments. I demonstrate the population of these states through the ultraviolet excitation of weakly bound molecules. By using the same ultraviolet excitation scheme, I place a new upper-bound on the minimum energy required to ionize 85Rb2 molecules.

We study the photoassociative collisional loss of laser-cooled Rb atoms from a far-off resonance optical dipole force atom trap. We obtain a well-resolved photoassociation spectrum from 50 ${\mathrm{cm}}^{\mathrm{\ensuremath{-}}1}$ to 980 ${\mathrm{cm}}^{\mathrm{\ensuremath{-}}1}$ below the first excited dissociation limit of the

{\mathrm{Rb}}_{2}

molecule. Two vibrational series associated with excited

{\mathrm{Rb}}_{2}

$^{3}\mathrm{\ensuremath{\Sigma}}_{\mathit{g}}^{+}$ states are clearly visible. Oscillations in the associated Franck-Condon factors reflect the structure of the triplet ground state wave function. Our results clearly demonstrate the potential of photoassociation spectroscopy as a new probe of molecular structure.