The Chromium Dimer: Closing a Chapter of Quantum Chemistry
Abstract
The complex electronic structure and unusual potential energy curve of the chromium dimer have fascinated scientists for decades, with agreement between theory and experiment so far elusive. Here, we present a new ab initio simulation of the potential energy curve and vibrational spectrum that significantly improves on all earlier estimates. Our data support a shift in earlier experimental assignments of a cluster of vibrational frequencies by one quantum number. The new vibrational assignment yields an experimentally derived potential energy curve in quantitative agreement with theory across all bond lengths and across all measured frequencies. By solving this long-standing problem, our results raise the possibility of quantitative quantum chemical modeling of transition metal clusters with spectroscopic accuracy.
Additional Information
© 2022 The Authors. Published by American Chemical Society. Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works (https://creativecommons.org/licenses/by-nc-nd/4.0/). We thank Doreen Leopold and Alec Wodtke for helpful discussions. Work by G.K.C. was supported by the US National Science Foundation (NSF) via grant no. CHE2102505. G.K.C. acknowledges additional support from the Simons Foundation via the Many-Electron Collaboration and the Investigator Award. Work by H.R.L., H.Z., and C.J.U. was supported by the Air Force Office of Scientific Research, under Award FA9550-18-1-0095. H.R.L. acknowledges support from a postdoctoral fellowship from the German Research Foundation (DFG) via grant LA 4442/1-1 during the first part of this work. Some of the computations were conducted at the Resnick High Performance Computing Center, a facility supported by the Resnick Sustainability Institute at the California Institute of Technology. The SHCI calculations were performed on the Bridges computer at the Pittsburgh Supercomputing Center under grant PHY170037. Data for reproducing Figure 2a is available at https://github.com/h-larsson/Cr2Pes22. Further data is available from the authors upon reasonable request. The authors declare the following competing financial interest(s): G.K.C. is part-owner of QSimulate, Inc.Attached Files
Published - ja2c06357.pdf
Supplemental Material - ja2c06357_si_001.pdf
Files
Name | Size | Download all |
---|---|---|
md5:84258f3639a53351dd1d288b2f4df6b9
|
595.6 kB | Preview Download |
md5:2fd363afa27acf7518d0c8b99c4da636
|
1.5 MB | Preview Download |
Additional details
- PMCID
- PMC9460780
- Eprint ID
- 116716
- Resolver ID
- CaltechAUTHORS:20220908-232209149
- NSF
- CHE-2102505
- Simons Foundation
- Air Force Office of Scientific Research (AFOSR)
- FA9550-18-1-0095
- Deutsche Forschungsgemeinschaft (DFG)
- LA 4442/1-1
- Resnick Sustainability Institute
- NSF
- PHY-170037
- Created
-
2022-09-08Created from EPrint's datestamp field
- Updated
-
2023-07-06Created from EPrint's last_modified field
- Caltech groups
- Resnick Sustainability Institute