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Title: Quantum computation solves a half-century-old enigma: Elusive vibrational states of magnesium dimer found

Abstract

The high-lying vibrational states of the magnesium dimer (Mg2), which has been recognized as an important system in studies of ultracold and collisional phenomena, have eluded experimental characterization for half a century. Until now, only the first 14 vibrational states of Mg2 have been experimentally resolved, although it has been suggested that the ground-state potential may support five additional levels. Here, we present highly accurate ab initio potential energy curves based on state-of-the-art coupled-cluster and full configuration interaction computations for the ground and excited electronic states involved in the experimental investigations of Mg2. Our ground-state potential unambiguously confirms the existence of 19 vibrational levels, with ~1 cm-1 root mean square deviation between the calculated rovibrational term values and the available experimental and experimentally derived data. Our computations reproduce the latest laser-induced fluorescence spectrum and provide guidance for the experimental detection of the previously unresolved vibrational levels.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]
  1. Michigan State University, East Lansing, MI (United States). Department of Chemistry
  2. Michigan State University, East Lansing, MI (United States). Department of Chemistry; Michigan State University, East Lansing, MI (United States). Department of Physics and Astronomy
Publication Date:
Research Org.:
Michigan State Univ., East Lansing, MI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF); USDOE Office of Science (SC)
OSTI Identifier:
1626039
Alternate Identifier(s):
OSTI ID: 1823407
Grant/Contract Number:  
FG02-01ER15228; CHE-1763371
Resource Type:
Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 6; Journal Issue: 14; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; Science & Technology - Other Topics; magnesium dimer; ab initio electronic structure calculations; potential energy surfaces; rovibrational states; rovibronic transitions; laser-induced fluorescence spectra; coupled-cluster theory; full configuration interaction

Citation Formats

Yuwono, Stephen H., Magoulas, Ilias, and Piecuch, Piotr. Quantum computation solves a half-century-old enigma: Elusive vibrational states of magnesium dimer found. United States: N. p., 2020. Web. doi:10.1126/sciadv.aay4058.
Yuwono, Stephen H., Magoulas, Ilias, & Piecuch, Piotr. Quantum computation solves a half-century-old enigma: Elusive vibrational states of magnesium dimer found. United States. https://doi.org/10.1126/sciadv.aay4058
Yuwono, Stephen H., Magoulas, Ilias, and Piecuch, Piotr. Fri . "Quantum computation solves a half-century-old enigma: Elusive vibrational states of magnesium dimer found". United States. https://doi.org/10.1126/sciadv.aay4058. https://www.osti.gov/servlets/purl/1626039.
@article{osti_1626039,
title = {Quantum computation solves a half-century-old enigma: Elusive vibrational states of magnesium dimer found},
author = {Yuwono, Stephen H. and Magoulas, Ilias and Piecuch, Piotr},
abstractNote = {The high-lying vibrational states of the magnesium dimer (Mg2), which has been recognized as an important system in studies of ultracold and collisional phenomena, have eluded experimental characterization for half a century. Until now, only the first 14 vibrational states of Mg2 have been experimentally resolved, although it has been suggested that the ground-state potential may support five additional levels. Here, we present highly accurate ab initio potential energy curves based on state-of-the-art coupled-cluster and full configuration interaction computations for the ground and excited electronic states involved in the experimental investigations of Mg2. Our ground-state potential unambiguously confirms the existence of 19 vibrational levels, with ~1 cm-1 root mean square deviation between the calculated rovibrational term values and the available experimental and experimentally derived data. Our computations reproduce the latest laser-induced fluorescence spectrum and provide guidance for the experimental detection of the previously unresolved vibrational levels.},
doi = {10.1126/sciadv.aay4058},
journal = {Science Advances},
number = 14,
volume = 6,
place = {United States},
year = {2020},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Figures / Tables:

Fig. 1 Fig. 1: The wave functions of the high-lying, purely vibrational, states of 24Mg2 and the underlying X 1 Σ$_{g} ^{+}$ potential. The last experimentally observed v″ = 13 level is marked in blue, the predicted v″ = 14 to 18 levels are marked in green, and the ab initio Xmore » 1 Σ$_{g} ^{+}$  PEC obtained in this study is marked by a long-dashed black line. The inset is a Birge-Sponer plot comparing the rotationless G(v″ + 1) − G(v″) energy differences as functions of v″ + ½ obtained in this work (black circles) with their experimentally derived counterparts (red open squares) based on the data reported in (12) (v″ = 0 to 12) and (17) (v″ = 13; cf. also Table 1). The red solid line is a linear fit of the experimental points.« less

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