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CASPT2 molecular geometries of Fe(II) spin-crossover complexes

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/d1cp04885f· OSTI ID:1978763
 [1];  [2];  [2];  [2]
  1. University of South Dakota, Vermillion, SD (United States); OSTI
  2. University of South Dakota, Vermillion, SD (United States)
+ Show Author Affiliations
Using fully internally contracted (FIC)-CASPT2 analytical gradients, geometry optimizations of spin-crossover complexes are reported. This approach is tested on a series of Fe(II) complexes with different sizes, ranging from 13 to 61 atoms. A combination of active space and basis set choices are employed to investigate their role in determining reliable molecular geometries. The reported strategy demonstrates that a wave function-based level of theory can be used to optimize the geometries of metal complexes in reasonable times and enables one to treat the molecular geometry and electronic structure of the complexes using the same level of theory. For a series of smaller Fe(II) SCO complexes, strong field ligands in the LS state result in geometries with the largest differences between DFT and CASPT2; however, good agreement overall is observed between DFT and CASPT2. For the larger complexes, moderate sized basis sets yield geometries that compare well with DFT and available experimental data. Here we recommend using the (10e,12o) active space since convergence to a minimum structure was more efficient than with truncated active spaces despite having similar Fe–ligand bond distances.
Research Organization:
University of California, Oakland, CA (United States); University of South Dakota, Vermillion, SD (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE; USDOE Office of Science (SC)
Grant/Contract Number:
AC02-05CH11231; SC0019463
OSTI ID:
1978763
Alternate ID(s):
OSTI ID: 1838238
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 3 Vol. 24; ISSN 1463-9076
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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