TY - JOUR
T1 - Performance Analysis and Optimization of Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory (MRSF-TDDFT) for Vertical Excitation Energies and Singlet-Triplet Energy Gaps
AU - Horbatenko, Yevhen
AU - Lee, Seunghoon
AU - Filatov, Michael
AU - Choi, Cheol Ho
N1 - Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/9/19
Y1 - 2019/9/19
N2 - The mixed-reference spin-flip (MRSF) time-dependent density functional theory (TDDFT) method eliminates the notorious spin contamination of SF-TDDFT, thus enabling identification of states of proper spin-symmetry for automatic geometry optimization and molecular dynamics simulations. Here, we analyze and optimize the MRSF-TDDFT in the calculations of the vertical excitation energies (VEEs) and the singlet-triplet (ST) gaps. The dependence of the obtained VEEs and ST gaps on the intrinsic parameters of the MRSF-TDDFT method is investigated, and prescriptions for the proper use of the method are formulated. For VEEs, MRSF-TDDFT displays similar or better accuracy than SF-TDDFT (ca. 0.5 eV), while considerably outperforming the LR-TDDFT for the ST gaps. As a result, a new functional of STG1X (dubbed here), especially for ST gaps is suggested on the basis of splitting between the components of the atomic multiplets.
AB - The mixed-reference spin-flip (MRSF) time-dependent density functional theory (TDDFT) method eliminates the notorious spin contamination of SF-TDDFT, thus enabling identification of states of proper spin-symmetry for automatic geometry optimization and molecular dynamics simulations. Here, we analyze and optimize the MRSF-TDDFT in the calculations of the vertical excitation energies (VEEs) and the singlet-triplet (ST) gaps. The dependence of the obtained VEEs and ST gaps on the intrinsic parameters of the MRSF-TDDFT method is investigated, and prescriptions for the proper use of the method are formulated. For VEEs, MRSF-TDDFT displays similar or better accuracy than SF-TDDFT (ca. 0.5 eV), while considerably outperforming the LR-TDDFT for the ST gaps. As a result, a new functional of STG1X (dubbed here), especially for ST gaps is suggested on the basis of splitting between the components of the atomic multiplets.
UR - http://www.scopus.com/inward/record.url?scp=85072508542&partnerID=8YFLogxK
U2 - 10.1021/acs.jpca.9b07556
DO - 10.1021/acs.jpca.9b07556
M3 - Article
C2 - 31436418
AN - SCOPUS:85072508542
SN - 1089-5639
VL - 123
SP - 7991
EP - 8000
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 37
ER -