Exact-Two-Component Multiconfiguration Pair-Density Functional Theory

Prachi Sharma, Andrew J. Jenkins, Giovanni Scalmani, Michael J. Frisch, Donald G. Truhlar, Laura Gagliardi, Xiaosong Li

Research output: Contribution to journalArticlepeer-review

9 Scopus citations


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 languageEnglish (US)
JournalJournal of Chemical Theory and Computation
Issue number5
StateAccepted/In press - 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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