Absorption spectrum of Ca atoms attached to $^4$He nanodroplets

TL;DR

This study uses density functional theory and ab-initio potentials to analyze the structure and absorption spectra of calcium atoms attached to helium-4 nanodroplets, exploring solvation, thermal effects, and vortex structures.

Contribution

It provides a detailed theoretical analysis of Ca atoms on helium droplets, including structure, spectra, and vortex effects, with new ab-initio potentials and insights into vortex detectability.

Findings

Good agreement with experimental absorption data

Thermal motion contributes about 10% to line broadening

Vortices are unlikely to be detected via spectroscopy

Abstract

Within density functional theory, we have obtained the structure of $^4$He droplets doped with neutral calcium atoms. These results have been used, in conjunction with newly determined {\it ab-initio} $^1\Sigma$ and $^1\Pi$ Ca-He pair potentials, to address the $4s4p$ $^1$P$_1 \leftarrow 4s^2$ $^1$S$_0$ transition of the attached Ca atom, finding a fairly good agreement with absorption experimental data. We have studied the drop structure as a function of the position of the Ca atom with respect of the center of mass of the helium moiety. The interplay between the density oscillations arising from the helium intrinsic structure and the density oscillations produced by the impurity in its neighborhood plays a role in the determination of the equilibrium state, and hence in the solvation properties of alkaline earth atoms. In a case of study, the thermal motion of the impurity within the drop surface region has been analyzed in a semi-quantitative way. We have found that, although the atomic shift shows a sizeable dependence on the impurity location, the thermal effect is statistically small, contributing by about a 10% to the line broadening. The structure of vortices attached to the calcium atom has been also addressed, and its effect on the calcium absorption spectrum discussed. At variance with previous theoretical predictions, we conclude that spectroscopic experiments on Ca atoms attached to $^4$He drops will be likely unable to detect the presence of quantized vortices in helium nanodrops.