| Autor: |
Prachi Sharma, Andrew J. Jenkins, Giovanni Scalmani, Michael J. Frisch, Donald G. Truhlar, Laura Gagliardi, Xiaosong Li |
| Rok vydání: |
2022 |
| Předmět: |
|
| Zdroj: |
Journal of chemical theory and computation. 18(5) |
| ISSN: |
1549-9626 |
| Popis: |
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. |
| Databáze: |
OpenAIRE |
| Externí odkaz: |
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