Calculation of Metallocene Ionization Potentials via Auxiliary Field Quantum Monte Carlo: Toward Benchmark Quantum Chemistry for Transition Metals

• Published in: Journal of chemical theory and computation Vol. 18; no. 5; pp. 2845 - 2862
• Main Authors: Rudshteyn, Benjamin, Weber, John L., Coskun, Dilek, Devlaminck, Pierre A., Zhang, Shiwei, Reichman, David R., Shee, James, Friesner, Richard A.
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 10.05.2022
• Subjects: Adiabatic flow; Chemistry; Coordination compounds; Density functional theory; Electrochemistry; Ionization potentials; Materials science; Mathematical analysis; Physics; Quantum chemistry; Quantum Electronic Structure; Solvation; Transition metal compounds; Vapor phases; Wave functions
• ISSN: 1549-9618; 1549-9626; 1549-9626
• DOI: 10.1021/acs.jctc.1c01071

The accurate ab initio prediction of ionization energies is essential to understanding the electrochemistry of transition metal complexes in both materials science and biological applications. However, such predictions have been complicated by the scarcity of gas phase experimental data, the relatively large size of the relevant molecules, and the presence of strong electron correlation effects. In this work, we apply all-electron phaseless auxiliary-field quantum Monte Carlo (ph-AFQMC) utilizing multideterminant trial wave functions to six metallocene complexes to compare the computed adiabatic and vertical ionization energies with experimental results. We find that ph-AFQMC yields mean absolute errors (MAEs) of 1.69 ± 1.02 kcal/mol for the adiabatic energies and 2.85 ± 1.13 kcal/mol for the vertical energies. We also carry out density functional theory (DFT) calculations using a variety of functionals, which yields MAEs of 3.62–6.98 kcal/mol and 3.31–9.88 kcal/mol, as well as one variant of localized coupled cluster calculations (DLPNO-CCSD­(T0) with moderate PNO cutoffs), which has MAEs of 4.96 and 6.08 kcal/mol, respectively. We also test the reliability of DLPNO-CCSD­(T0) and DFT on acetylacetonate (acac) complexes for adiabatic energies measured in the same manner experimentally, and we find higher MAEs, ranging from 4.56 to 10.99 kcal/mol (with a different ordering) for DFT and 6.97 kcal/mol for DLPNO-CCSD­(T0). Finally, by utilizing experimental solvation energies, we show that accurate reduction potentials in solution for the metallocene series can be obtained from the AFQMC gas phase results.