Abstract
Molecules containing late-row elements exhibit large relativistic effects. To account for both relativistic effects and electron correlation in a computationally inexpensive way, we derived a formulation of multiconfiguration pair-density functional theory with the relativistic exact-two-component Hamiltonian (X2C-MC-PDFT). In this new method, relativistic effects are included during variational optimization of a reference wave function by exact-two-component complete active-space self-consistent-field (X2C-CASSCF) theory, followed by an energy evaluation using pair-density functional theory. Benchmark studies of excited-state and ground-state fine-structure splitting of atomic species show that X2C-MC-PDFT can significantly improve the X2C-CASSCF results by introducing additional state-specific electron correlation.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 2947-2954 |
| Number of pages | 8 |
| Journal | Journal of Chemical Theory and Computation |
| Volume | 18 |
| Issue number | 5 |
| DOIs | |
| State | Published - May 10 2022 |
Bibliographical note
Funding Information:The development of variational spin–orbit methods for computing excited-state couplings and magnetic properties is supported by the Air Force Office of Scientific Research (grant no. FA9550-21-1-0344 to X.L. and FA9550-20-1-0360 to L.G. and D.G.T.).
Publisher Copyright:
© 2022 American Chemical Society.
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