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

doi:10.1021/acs.jctc.2c00062

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 journal › Article › peer-review

1 Scopus citations

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)
Journal	Journal of Chemical Theory and Computation
Volume	18
Issue number	5
DOIs	https://doi.org/10.1021/acs.jctc.2c00062
State	Accepted/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.).

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© 2022 American Chemical Society.

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10.1021/acs.jctc.2c00062

Cite this

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title = "Exact-Two-Component Multiconfiguration Pair-Density Functional Theory",

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.",

author = "Prachi Sharma and Jenkins, {Andrew J.} and Giovanni Scalmani and Frisch, {Michael J.} and Truhlar, {Donald G.} and Laura Gagliardi and Xiaosong Li",

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: {\textcopyright} 2022 American Chemical Society.",

year = "2022",

doi = "10.1021/acs.jctc.2c00062",

language = "English (US)",

volume = "18",

journal = "Journal of Chemical Theory and Computation",

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T1 - Exact-Two-Component Multiconfiguration Pair-Density Functional Theory

AU - Sharma, Prachi

AU - Jenkins, Andrew J.

AU - Scalmani, Giovanni

AU - Frisch, Michael J.

AU - Truhlar, Donald G.

AU - Gagliardi, Laura

AU - Li, Xiaosong

N1 - 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.

PY - 2022

Y1 - 2022

N2 - 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.

AB - 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.

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U2 - 10.1021/acs.jctc.2c00062

DO - 10.1021/acs.jctc.2c00062

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SN - 1549-9618

VL - 18

JO - Journal of Chemical Theory and Computation

JF - Journal of Chemical Theory and Computation

IS - 5

ER -

Exact-Two-Component Multiconfiguration Pair-Density Functional Theory

Abstract

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