TY - JOUR
T1 - UMRSF-TDDFT
T2 - Unrestricted Mixed-Reference Spin-Flip-TDDFT
AU - Komarov, Konstantin
AU - Oh, Minseok
AU - Nakata, Hiroya
AU - Lee, Seunghoon
AU - Choi, Cheol Ho
N1 - Publisher Copyright:
© 2024 American Chemical Society.
PY - 2024/10/31
Y1 - 2024/10/31
N2 - An unrestricted version of Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory (UMRSF-TDDFT) was developed based on unrestricted Kohn-Sham orbitals (UKS) with a new molecular orbital (MO) reordering scheme. Additionally, a simple yet accurate method for estimating ⟨S2⟩ expectation values was devised. UMRSF-TDDFT was benchmarked against cases where DFT, TDDFT, and SF-TDDFT traditionally fail to provide accurate descriptions. In an application to the ground and excited states of a Be atom, UMRSF-TDDFT successfully recovers the degenerate states, with its energies slightly reduced compared to its RO counterpart, due to the additional variational flexibility of UKS. A clear difference between UMRSF and U-SF-TDDFT is evident in the bond breaking of the hydrogen fluoride system, as the latter misses an important configuration. In the case of the Jahn-Teller distortion of trimethylenemethane (TMM), the relative singlet energy compared to the triplet is lower by 0.1 and 0.2 eV for UMRSF and U-SF-TDDFT, respectively, than that of MRSF-TDDFT. The reduction in UMRSF energy is attributed to spatial orbital relaxations, whereas the reduction in U-SF-TDDFT energy results from spin contamination. Overall, the additional orbital relaxations afforded by unrestricted Kohn-Sham (UKS) orbitals in UMRSF-TDDFT lead to lower total system energies compared to their restricted open-shell counterparts. This enhancement adds a practical and accurate quantum chemical theory to the existing RO variant for addressing challenging systems where traditional quantum theories suffer.
AB - An unrestricted version of Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory (UMRSF-TDDFT) was developed based on unrestricted Kohn-Sham orbitals (UKS) with a new molecular orbital (MO) reordering scheme. Additionally, a simple yet accurate method for estimating ⟨S2⟩ expectation values was devised. UMRSF-TDDFT was benchmarked against cases where DFT, TDDFT, and SF-TDDFT traditionally fail to provide accurate descriptions. In an application to the ground and excited states of a Be atom, UMRSF-TDDFT successfully recovers the degenerate states, with its energies slightly reduced compared to its RO counterpart, due to the additional variational flexibility of UKS. A clear difference between UMRSF and U-SF-TDDFT is evident in the bond breaking of the hydrogen fluoride system, as the latter misses an important configuration. In the case of the Jahn-Teller distortion of trimethylenemethane (TMM), the relative singlet energy compared to the triplet is lower by 0.1 and 0.2 eV for UMRSF and U-SF-TDDFT, respectively, than that of MRSF-TDDFT. The reduction in UMRSF energy is attributed to spatial orbital relaxations, whereas the reduction in U-SF-TDDFT energy results from spin contamination. Overall, the additional orbital relaxations afforded by unrestricted Kohn-Sham (UKS) orbitals in UMRSF-TDDFT lead to lower total system energies compared to their restricted open-shell counterparts. This enhancement adds a practical and accurate quantum chemical theory to the existing RO variant for addressing challenging systems where traditional quantum theories suffer.
UR - http://www.scopus.com/inward/record.url?scp=85206994537&partnerID=8YFLogxK
U2 - 10.1021/acs.jpca.4c04521
DO - 10.1021/acs.jpca.4c04521
M3 - Article
C2 - 39415560
AN - SCOPUS:85206994537
SN - 1089-5639
VL - 128
SP - 9526
EP - 9537
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 43
ER -