Accurate Spin–Orbit Coupling by Relativistic Mixed-Reference Spin-Flip-TDDFT

Komarov, Konstantin; Park, Woojin; Lee, Seung‐Hoon; Zeng, Tao; Choi, Cheol Ho

doi:10.1021/acs.jctc.2c01036

Cited by 13 publications

(27 citation statements)

References 95 publications

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“…To alleviate the situation, recently, some of us have explored the optimization of XC functionals for MRSF, 19 where it was shown that significant prediction accuracy improvements can be achieved with the help of a "double tuning" idea. Rather than utilizing the same XC functionals during the entire computational process, the use of adaptive XC functionals was attempted for the reference Kohn−Sham (KS) DFT and the response part of calculations, respectively.…”

Section: ■ Introductionmentioning

confidence: 99%

“…20 The "double tuning" idea in the framework of the Coulomb-attenuated method (CAM) functional yielded two new XC functionals of the doubly tuned Coulomb-attenuated method, (DTCAM)-VEE and DTCAM-AEE, for vertical excitation energies (VEEs). 19 T h i s c o n t e n t i s In the current paper, further investigations shall be performed toward consistent predictions of both core/valence ionization potentials (cIPs/vIPs) and VEEs in the search for universally useful XC functionals for MRSF. As X-ray light sources with an intense and coherent pulse like X-ray freeelectron lasers 21 are becoming available, significant attention has been directed to X-ray spectroscopy, 22 leading to the timeresolved (TR) variants of X-ray absorption spectroscopy (XAS), photoelectron spectroscopy (XPS), etc.…”

Section: ■ Introductionmentioning

confidence: 99%

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Toward Consistent Predictions of Core/Valence Ionization Potentials and Valence Excitation Energies by MRSF-TDDFT

Park,

Lashkaripour,

Komarov

et al. 2024

J. Chem. Theory Comput.

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Optimizing exchange−correlation functionals for both core/valence ionization potentials (cIPs/vIPs) and valence excitation energies (VEEs) at the same time in the framework of MRSF-TDDFT is self-contradictory. To overcome the challenge, within the previous "adaptive exact exchange" or double-tuning strategy on Coulomb-attenuating XC functionals (CAM), a new XC functional specifically for cIPs and vIPs was first developed by enhancing exact exchange to both short-and long-range regions. The resulting DTCAM-XI functional achieved remarkably high accuracy in its predictions with errors of less than half eV. An additional concept of "valence attenuation", where the amount of exact exchange for the frontier orbital regions is selectively suppressed, was introduced to consistently predict both VEEs and IPs at the same time. The second functional, DTCAM-XIV, exhibits consistent overall prediction accuracy at ∼0.64 eV. By preferentially optimizing VEEs within the same "valence attenuation" concept, a third functional, DTCAM-VAEE, was obtained, which exhibits improved performance as compared to that of the previous DTCAM-VEE and DTCAM-AEE in the prediction of VEEs, making it an attractive alternative to BH&HLYP. As the combination of "adaptive exchange" and "valence attenuation" is operative, it would be exciting to explore its potential with a more tunable framework in the future.

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Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Toward Consistent Predictions of Core/Valence Ionization Potentials and Valence Excitation Energies by MRSF-TDDFT

Park,

Lashkaripour,

Komarov

et al. 2024

J. Chem. Theory Comput.

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“…12 Therefore, after its initial introductions, the MRSF-TDDFT 27,29 has proven to be a promising quantum theory for general use, overcoming the major issues of existing theories. In a series of studies, [30][31][32][33][34][35][36][37][38][39][40] it has been demonstrated that the MRSF-TDDFT approach can also yield accurate nonadiabatic coupling matrix elements (NACMEs) 35,36 enabling reliable nonadiabatic molecular dynamics (NAMD) simulations, 39,[41][42][43][44][45][46] accurate spin-orbit couplings (SOC) 47 and very accurate X-ray absorption predictions. 48 This method has also been successfully used in designing highly performing optoelectronic materials.…”

Section: Introductionsmentioning

confidence: 99%

Doubly Tuned Exchange-Correlation Functionals for Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory

Komarov

Park

Lee

et al. 2023

Preprint

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It is demonstrated that significant accuracy improvements of MRSF-TDDFT can be achieved by introducing two different XC functionals for the reference Kohn-Sham DFT and the response part of calculations, respectively. Accordingly, two new exchange-correlation (XC) functionals of DTCAM-VEE and DTCAM-AEE were developed on the basis of the "adaptive exact exchange (AEE)" concept in the framework of the Coulomb-attenuating XC functionals. The values by DTCAM-VEE are in excellent agreement with those of Thiel's set (mean absolute error (MAE) and interquartile range (IQR) of 0.218 and 0.327 eV, respectively). On the other hand, DTCAM-AEE faithfully reproduced the qualitative aspects of conical intersections of trans-butadiene and thymine, and the NAMD simulations on thymine. The latter functional also remarkably exhibited the exact 1/R asymptotic behavior of the charge-transfer state of an ethylene-tetrafluoroethylene dimer, and the accurate potential energy surfaces along the two torsional angles of retinal protonated Schiff base model with six double bonds (rPSB6). The current idea can be also applied to other XC functionals as well as other variants of linear response theories, opening a new way of developing XC functionals.

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“…Therefore, after its initial introductions, the MRSF-TDDFT , has proven to be a promising quantum theory for general use, overcoming the major issues of existing theories. In a series of studies, − it has been demonstrated that the MRSF-TDDFT approach can also yield accurate nonadiabatic coupling matrix elements (NACMEs) , enabling reliable nonadiabatic molecular dynamics (NAMD) simulations, ,− accurate spin–orbit couplings (SOC), and very accurate X-ray absorption predictions . This method has also been successfully used in designing highly performing optoelectronic materials. ,− The MRSF-TDDFT has finally been released publicly by GAMESS (July 31, 2022 R1 Public Release Version) …”

Section: Introductionsmentioning

confidence: 99%

Doubly Tuned Exchange–Correlation Functionals for Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory

Komarov,

Park,

Lee

et al. 2023

J. Chem. Theory Comput.

Self Cite

View full text Add to dashboard Cite

It is demonstrated that significant accuracy improvements in MRSF-TDDFT can be achieved by introducing two different exchange−correlation (XC) functionals for the reference Kohn−Sham DFT and the response part of the calculations, respectively. Accordingly, two new XC functionals of doubly tuned Coulomb attenuated method-vertical excitation energy (DTCAM-VEE) and DTCAM-AEE were developed on the basis of the "adaptive exact exchange (AEE)" concept in the framework of the Coulomb-attenuating XC functionals. The values by DTCAM-VEE are in excellent agreement with those of Thiel's set [mean absolute errors (MAEs) and the interquartile range (IQR) values of 0.218 and 0.327 eV, respectively]. On the other hand, DTCAM-AEE faithfully reproduced the qualitative aspects of conical intersections (CIs) of transbutadiene and thymine and the nonadiabatic molecular dynamics (NAMD) simulations on thymine. The latter functional also remarkably exhibited the exact 1/R asymptotic behavior of the charge-transfer state of an ethylene−tetrafluoroethylene dimer and the accurate potential energy surfaces (PESs) along the two torsional angles of retinal protonated Schiff base model with six double bonds (rPSB6). Overall, DTCAM-AEE generally performs well, as its MAE (0.237) and IQR (0.41 eV) are much improved as compared to BH&HLYP. The current idea can also be applied to other XC functionals as well as other variants of linear response theories, opening a new way of developing XC functionals. ■ INTRODUCTIONSA widely used methodology for studying molecular excited states is the spin-conserving linear response time-dependent density functional theory (LR-TDDFT). 1−3 Despite the success of conventional LR-TDDFT in describing the lowlying excitation energies of molecules, there are well-known limitations. These include the energy of long-range charge transfer excitations within pure and hybrid exchange− correlation (XC) functionals, 4−8 excited states with substantial double excitation character, 9−12 states of molecules undergoing bond breaking, 13,14 and the topology of conical intersections (CIs). 15−18 There have been various attempts to address the issues of charge transfer 19,20 and double excitations. 10,21,22 These limitations can also be overcome more explicitly by the spin-flip model, 23 especially the spin-flip (SF)-TDDFT, 24−27 which utilizes spin-flip excitations from high spin triplet reference (M s = +1). Thus, the incorrect description of the CI, single bond breaking, and the poor description of multireference electronic states can be corrected by it. 24−26 However, SF-TDDFT may suffer from considerable spin contamination. 28−30 As it is due to the incomplete configurations of its response space, a fundamental solution to the problem is to include the missing ones. However, unlike wave function theories, a considerable challenge remains with respect to TDDFT when going beyond the adiabatic approximation to account for more than single excitations. 21 The introduction of the tensor equation-of-motion (TEOM)

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Accurate Spin–Orbit Coupling by Relativistic Mixed-Reference Spin-Flip-TDDFT

Cited by 13 publications

References 95 publications

Toward Consistent Predictions of Core/Valence Ionization Potentials and Valence Excitation Energies by MRSF-TDDFT

Toward Consistent Predictions of Core/Valence Ionization Potentials and Valence Excitation Energies by MRSF-TDDFT

Doubly Tuned Exchange-Correlation Functionals for Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory

Doubly Tuned Exchange–Correlation Functionals for Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory

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