Minimum-Energy Conical Intersections by Compressed Multistate Pair-Density Functional Theory

Calio, Paul B.Univ Chicago, James Franck Inst, Chicago Ctr Theoret Chem, Chicago Ctr Theoret Chem,Dept Chem, Chicago, IL 60637 USA. (author)

Compressed multistate pair-density functional theory (CMS-PDFT) is a multistate version of multiconfiguration pair-density functional theory that can capture the correct topology of coupled potential energy surfaces (PESs) around conical intersections. In this work, we develop interstate coupling vectors (ISCs) for CMS-PDFT in the OpenMolcas and PySCF/mrh electronic structure packages. Yet, the main focus of this work is using ISCs to calculate minimum-energy conical intersections (MECIs) by CMS-PDFT. This is performed using the projected constrained optimization method in OpenMolcas, which uses ISCs to restrain the iterations to the conical intersection seam. We optimize the S1/S0 MECIs for ethylene, butadiene, and benzene and show that CMS-PDFT gives smooth PESs in the vicinities of the MECIs. Furthermore, the CMS-PDFT MECIs are in good agreement with the MECI calculated by the more expensive XMS-CASPT2 method.

Hermes, Matthew R.Univ Chicago, James Franck Inst, Chicago Ctr Theoret Chem, Chicago Ctr Theoret Chem,Dept Chem, Chicago, IL 60637 USA. (author)
Bao, Jie J.Univ Minnesota, Chem Theory Ctr, Dept Chem, Minneapolis, MN 55455 USA.;Univ Minnesota, Minnesota Supercomp Inst, Minneapolis, MN 55455 USA. (author)
Fernández Galván, Ignacio,1977-Uppsala universitet,Organisk kemi(Swepub:uu)ignga749 (author)
Lindh, Roland,Professor,1958-Uppsala universitet,Organisk kemi(Swepub:uu)rolli621 (author)
Truhlar, Donald G.Univ Minnesota, Chem Theory Ctr, Dept Chem, Minneapolis, MN 55455 USA.;Univ Minnesota, Minnesota Supercomp Inst, Minneapolis, MN 55455 USA. (author)
Gagliardi, LauraUniv Chicago, James Franck Inst, Chicago Ctr Theoret Chem, Chicago Ctr Theoret Chem,Dept Chem, Chicago, IL 60637 USA.;Argonne Natl Lab, Lemont, IL 60439 USA. (author)
Univ Chicago, James Franck Inst, Chicago Ctr Theoret Chem, Chicago Ctr Theoret Chem,Dept Chem, Chicago, IL 60637 USA.Univ Minnesota, Chem Theory Ctr, Dept Chem, Minneapolis, MN 55455 USA.;Univ Minnesota, Minnesota Supercomp Inst, Minneapolis, MN 55455 USA. (creator_code:org_t)

In:Journal of Physical Chemistry A: American Chemical Society (ACS)128:9, s. 1698-17061089-56391520-5215

By the author/editor: Calio, Paul B.; Hermes, Matthew ...; Bao, Jie J.; Fernández Galván ...; Lindh, Roland, P ...; Truhlar, Donald ...; show more...; Gagliardi, Laura; show less...

About the subject

NATURAL SCIENCES: NATURAL SCIENCES; and Chemical Science ...; and Theoretical Chem ...

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