Resonance between electronic and rotational motions in Rydberg states of CaF

Kay, Jeffrey J; Altunata, Serhan N.; Coy, Stephen L.; Field, Robert W.

doi:10.1080/00268970701549371

Cited by 12 publications

(8 citation statements)

References 25 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[4][5][6][7][8] When electronic motion tunes into resonance with another motion, energy exchange between the Rydberg electron and the molecular ion-core becomes rapid and efficient, resulting in extensively fragmented energy level patterns and a nearcomplete loss of regularity. The Born-Oppenheimer approximation works well at low energy, where the mismatch in timescales of electronic and nuclear motions prevents interconversion of energy, and the intramolecular dynamics is simple and usually restricted to one potential energy surface.…”

Section: Introductionmentioning

confidence: 99%

A quantum defect model for the s, p, d, and f Rydberg series of CaF

Kay

Coy

Wong

et al. 2011

The Journal of Chemical Physics

Self Cite

View full text Add to dashboard Cite

We present an improved quantum defect theory model for the "s," "p," "d," and "f" Rydberg series of CaF. The model, which is the result of an exhaustive fit of high-resolution spectroscopic data, parameterizes the electronic structure of the ten ("s"Σ, "p"Σ, "p"Π, "d"Σ, "d"Π, "d"Δ, "f"Σ, "f"Π, "f"Δ, and "f"Φ) Rydberg series of CaF in terms of a set of twenty μ(ll('))(Λ) quantum defect matrix elements and their dependence on both internuclear separation and on the binding energy of the outer electron. Over 1000 rovibronic Rydberg levels belonging to 131 observed electronic states of CaF with n∗ ≥ 5 are included in the fit. The correctness and physical validity of the fit model are assured both by our intuition-guided combinatorial fit strategy and by comparison with R-matrix calculations based on a one-electron effective potential. The power of this quantum defect model lies in its ability to account for the rovibronic energy level structure and nearly all dynamical processes, including structure and dynamics outside of the range of the current observations. Its completeness places CaF at a level of spectroscopic characterization similar to NO and H(2).

show abstract

Section: Introductionmentioning

confidence: 99%

A quantum defect model for the s, p, d, and f Rydberg series of CaF

Kay

Coy

Wong

et al. 2011

The Journal of Chemical Physics

Self Cite

View full text Add to dashboard Cite

show abstract

“…High resolution spectra of molecular Rydberg states will enable precision measurements of the properties of molecular cations, [1][2][3][4][5][6] highly efficient Stark slowing and trapping of neutral molecules, [7][8][9][10][11] and identification of the physical mechanisms of electron-ion energy transfer and reaction pathways in simple systems. [12][13][14][15][16][17][18][19][20][21][22] However, for nearly all molecules, the ionization threshold lies at a much higher energy than the dissociation threshold. As a result, long-lived Rydberg states can generally only be populated via sequential excitation steps through electronic states that are profoundly affected by rapid predissociation.…”

Section: Introductionmentioning

confidence: 99%

Coherent laser-millimeter-wave interactions en route to coherent population transfer

Grimes

Barnum

Zhou

et al. 2017

The Journal of Chemical Physics

Self Cite

View full text Add to dashboard Cite

We demonstrate coherent two-photon population transfer to Rydberg states of barium atoms using a combination of a pulsed dye laser and a chirped-pulse millimeter-wave spectrometer. Numerical calculations, using a density matrix formalism, reproduce our experimental results and explain the factors responsible for the observed fractional population transferred, optimal experimental conditions, and possibilities for future improvements. The long coherence times associated with the millimeter-wave radiation aid in creating coherence between the ground state and Rydberg states, but higher-coherence laser sources are required to achieve stimulated Raman adiabatic passage and for applications to molecules.

show abstract

“…In works [11,[26][27][28][29][30][31][32] the calculation was performed in the frame of BO approximation, effect of the core rotation was not taken into account there. The core rotation was considered in the works [12,33,34], but on the other hand the effect of long-range core dipole potential in IBO region was not consistently accounted for.…”

Section: Introductionmentioning

confidence: 99%