Zwitterions Functionalized by Optical Cycling Centers: Toward Laser-Coolable Polyatomic Molecular Cations.

Functionalization of large aromatic compounds and biomolecules with optical cycling centers (OCC) is of considerable interest for the design and engineering of molecules with a highly selective optical photoresponse. Both internal and external dynamics in such molecules can be precisely controlled by lasers, enabling their efficient cooling and opening up broad prospects for high-precision spectroscopy, ultracold chemistry, enantiomer separation, and various other fields. The way the OCC is bonded to a molecular ligand is crucial to the optical properties of the OCC, first of all, for the degree of closure of the optical cycling loop.

Accurate ab initio calculations of RaF electronic structure appeal to more laser-spectroscopical measurements.

Recently, a breakthrough has been achieved in laser-spectroscopic studies of short-lived radioactive compounds with the first measurements of the radium monofluoride molecule (RaF) UV/vis spectra. We report results from high-accuracy ab initio calculations of the RaF electronic structure for ground and low-lying excited electronic states. Two different methods agree excellently with experimental excitation energies from the electronic ground state to the Π and Π states, but lead consistently and unambiguously to deviations from experimental-based adiabatic transition energy estimates for the Σ excited electronic state, and show that more measurements are needed to clarify spectroscopic assignment of the Δ state.

Chiral Molecules as Sensitive Probes for Direct Detection of P-Odd Cosmic Fields.

Potential advantages of chiral molecules for a sensitive search for parity violating cosmic fields are highlighted. Such fields are invoked in different models for cold dark matter or in the Lorentz-invariance violating standard model extensions and thus are signatures of physics beyond the standard model. The sensitivity of a 20-year-old experiment with the molecule CHBrClF to pseudovector cosmic fields as characterized by the parameter |b_{0}^{e}| is estimated to be O(10^{-12}  GeV) employing ab initio calculations.

Towards Ultracold Chiral Molecules.

Atoms can be cooled and trapped efficiently with the help of lasers. So-called Doppler cooling takes advantage of momentum transfer upon absorption and emission of photons and of Doppler shifts to facilitate effectively closed optical absorption-emission loops, by which atoms are slowed down and cooled. Due to the wealth of internal degrees of freedom accessible in molecules, it was assumed for a long time that similarly closed optical loops cannot be realised for molecules.

Polyatomic Candidates for Cooling of Molecules with Lasers from Simple Theoretical Concepts.

A rational approach to identify polyatomic molecules that appear to be promising candidates for direct Doppler cooling with lasers is outlined. First-principles calculations for equilibrium structures and Franck-Condon factors of selected representatives with different point-group symmetries (including the chiral nonsymmetric C1) have been performed and a high potential for laser cooling of these molecules is indicated.