Issue 39, 2021

An efficient implementation of spin–orbit coupling within the framework of semiempirical orthogonalization-corrected methods for ultrafast intersystem crossing dynamics

Abstract

We implement spin–orbit coupling (SOC) within the framework of semiempirical orthogonalization-corrected methods (OMx). The excited-state wavefunction is generated from configuration interaction with single excitations (CIS). The SOC Hamiltonian in terms of the one-electron Breit–Pauli operator with effective nuclear charges is adopted in this work. Benchmark calculations show that SOCs evaluated using the OMx/CIS method agree very well with those obtained from time-dependent density functional theory. As a particularly attractive application, we incorporate SOCs between singlet and triplet states into Tully's fewest switches surface hopping algorithm to enable excited-state nonadiabatic dynamics simulations, treating internal conversion and intersystem crossing on an equal footing. This semiempirical dynamics simulation approach is applied to investigate ultrafast intersystem crossing processes in core-substituted naphthalenediimides.

Graphical abstract: An efficient implementation of spin–orbit coupling within the framework of semiempirical orthogonalization-corrected methods for ultrafast intersystem crossing dynamics

Supplementary files

Article information

Article type
Paper
Submitted
29 jul 2021
Accepted
12 set 2021
First published
14 set 2021

Phys. Chem. Chem. Phys., 2021,23, 22313-22323

An efficient implementation of spin–orbit coupling within the framework of semiempirical orthogonalization-corrected methods for ultrafast intersystem crossing dynamics

J. Liu, Z. Lan and J. Yang, Phys. Chem. Chem. Phys., 2021, 23, 22313 DOI: 10.1039/D1CP03477D

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