Excited Electronic States of Sr 2 : Ab Initio Predictions and Experimental Observation of the 2 1 Σ u + State

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 127; no. 20; pp. 4473 - 4482
• Main Authors: Szczepkowski, Jacek, Gronowski, Marcin, Grochola, Anna, Jastrzebski, Włodzimierz, Tomza, Michał, Kowalczyk, Paweł
• Format: Journal Article
• Language: English
• Published: United States 25-05-2023
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.3c02056

Despite its apparently simple nature with four valence electrons, the strontium dimer constitutes a challenge for modern electronic structure theory. Here we focus on excited electronic states of Sr
, which we investigate theoretically up to 25000 cm
above the ground state, to guide and explain new spectroscopic measurements. In particular, we focus on potential energy curves for the 1
Σ
, 2
Σ
, 1
Π
, 2
Π
, and 1
Δ
states computed using several variants of ab initio coupled-cluster and configuration-interaction methods to benchmark them. In addition, a new experimental study of the excited 2
Σ
state using polarization labeling spectroscopy is presented, which extends knowledge of this state to high vibrational levels, where perturbation by higher electronic states is observed. The available experimental observations are compared with the theoretical predictions and help to assess the accuracy and limitations of employed theoretical models. The present results pave the way for future more accurate theoretical and experimental spectroscopic studies.