Photodissociation spectra of single trapped CaOH+ molecular ions.

Molecular ions that are generated by chemical reactions with trapped atomic ions can serve as an accessible testbed for developing molecular quantum technologies. On the other hand, they are also a hindrance to scaling up quantum computers based on atomic ions, as unavoidable reactions with background gases destroy the information carriers. Here, we investigate the single- and two-photon dissociation processes of single CaOH+ molecular ions co-trapped in Ca+ ion crystals using a femtosecond laser system. We report the photodissociation cross section spectra of CaOH+ for single-photon processes at λ = 245-275 nm and for two-photon processes at λ = 500-540 nm. Measurements are interpreted with quantum-chemical calculations, which predict the photodissociation threshold for CaOH+ → Ca+ + OH at 265 nm. This result can serve as a basis for dissociation-based spectroscopy for studying the internal structure of CaOH+. The result also gives a prescription for recycling Ca+ ions in large-scale trapped Ca+ quantum experiments from undesired CaOH+ ions formed in the presence of background water vapor.

Symphony on strong field approximation.

This paper has been prepared by the Symphony collaboration (University of Warsaw, Uniwersytet Jagiellonski, DESY/CNR and ICFO) on the occasion of the 25th anniversary of the 'simple man's models' which underlie most of the phenomena that occur when intense ultrashort laser pulses interact with matter. The phenomena in question include high-harmonic generation (HHG), above-threshold ionization (ATI), and non-sequential multielectron ionization (NSMI). 'Simple man's models' provide both an intuitive basis for understanding the numerical solutions of the time-dependent Schrödinger equation and the motivation for the powerful analytic approximations generally known as the strong field approximation (SFA). In this paper we first review the SFA in the form developed by us in the last 25 years. In this approach the SFA is a method to solve the TDSE, in which the non-perturbative interactions are described by including continuum-continuum interactions in a systematic perturbation-like theory. In this review we focus on recent applications of the SFA to HHG, ATI and NSMI from multi-electron atoms and from multi-atom molecules. The main novel part of the presented theory concerns generalizations of the SFA to: (i) time-dependent treatment of two-electron atoms, allowing for studies of an interplay between electron impact ionization and resonant excitation with subsequent ionization; (ii) time-dependent treatment in the single active electron approximation of 'large' molecules and targets which are themselves undergoing dynamics during the HHG or ATI processes. In particular, we formulate the general expressions for the case of arbitrary molecules, combining input from quantum chemistry and quantum dynamics. We formulate also theory of time-dependent separable molecular potentials to model analytically the dynamics of realistic electronic wave packets for molecules in strong laser fields. We dedicate this work to the memory of Bertrand Carré, who passed away in March 2018 at the age of 60.

Exchange splitting of the interaction energy and the multipole expansion of the wave function.

The exchange splitting J of the interaction energy of the hydrogen atom with a proton is calculated using the conventional surface-integral formula Jsurf[Φ], the volume-integral formula of the symmetry-adapted perturbation theory JSAPT[Φ], and a variational volume-integral formula Jvar[Φ]. The calculations are based on the multipole expansion of the wave function Φ, which is divergent for any internuclear distance R. Nevertheless, the resulting approximations to the leading coefficient j0 in the large-R asymptotic series J(R) = 2e(-R-1)R(j0 + j1R(-1) + j2R(-2) + ⋯) converge with the rate corresponding to the convergence radii equal to 4, 2, and 1 when the Jvar[Φ], Jsurf[Φ], and JSAPT[Φ] formulas are used, respectively. Additionally, we observe that also the higher jk coefficients are predicted correctly when the multipole expansion is used in the Jvar[Φ] and Jsurf[Φ] formulas. The symmetry adapted perturbation theory formula JSAPT[Φ] predicts correctly only the first two coefficients, j0 and j1, gives a wrong value of j2, and diverges for higher jn. Since the variational volume-integral formula can be easily generalized to many-electron systems and evaluated with standard basis-set techniques of quantum chemistry, it provides an alternative for the determination of the exchange splitting and the exchange contribution of the interaction potential in general.