Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory for Accurate X-ray Absorption Spectroscopy

Park, Woojin; Alías-Rodríguez, Marc; Cho, Daeheum; Lee, Seunghoon; Huix‐Rotllant, Miquel; Choi, Cheol Ho

doi:10.1021/acs.jctc.2c00746

Cited by 15 publications

(25 citation statements)

References 77 publications

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“…This restricts the MRSF-TDDFT excitation space from unwanted occupied orbitals. This simple strategy exhibited near-perfect predictions with RMSE ∼ 0.5 eV, featuring a median value of 0.3 and an interquartile range of 0.4 for K-edge excitation energies of 24 s- and 17 third-row molecules …”

Section: Methodsmentioning

confidence: 99%

“…Our model is based on a combination of the electrostatic embedding QM/MM method, used to equilibrate a water droplet around the molecule of interest, and mixed-reference spin-flip time-dependent density functional theory (MRSF-TDDFT) coupled to QM/MM to extract X-ray spectroscopy. MRSF-TDDFT has been recently shown to be able to efficiently and accurately extract XAS, with errors that are within 1 eV of the experimental spectra . In addition, an MRSF-TDDFT/MM coupling was shown to lead to accurate excited-state nonadiabatic dynamics of thymine in water …”

Section: Introductionmentioning

confidence: 99%

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Solvent Effects and pH Dependence of the X-ray Absorption Spectra of Proline from Electrostatic Embedding Quantum Mechanics/Molecular Mechanics and Mixed-Reference Spin-Flip Time-dependent Density-Functional Theory

Alías-Rodríguez,

Bonfrate,

Park

et al. 2023

J. Phys. Chem. A

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The accurate description of solvent effects on X-ray absorption spectra (XAS) is fundamental for comparing simulated spectra with experiments in solution. Currently, few protocols exist that can efficiently reproduce the effects of the solute/solvent interactions on XAS. Here, we develop an efficient and accurate theoretical protocol for simulating the solvent effects on XAS. The protocol combines electrostatic embedding QM/MM based on electrostatic potential fitted (ESPF) operators for describing the solute/solvent interactions and mixed-reference spin-flip time-dependent density functional theory (MRSF-TDDFT) for simulating accurate XAS spectra. To demonstrate the capabilities of our protocol, we compute the X-ray absorption of neutral proline in the gas phase and ionic proline in water in all relevant K-edges, showing an excellent agreement with experiments. We show that states represented by core to π * transitions are almost unaffected by the interaction with water, whereas the core to σ * transitions are more impacted by the fluctuation of proline structure and the electrostatic interaction with the solvent. Finally, we reconstruct the pH-dependent X-ray absorption spectra of proline in solution, determining that the N K-edge can be used to distinguish its three protonation states.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Solvent Effects and pH Dependence of the X-ray Absorption Spectra of Proline from Electrostatic Embedding Quantum Mechanics/Molecular Mechanics and Mixed-Reference Spin-Flip Time-dependent Density-Functional Theory

Alías-Rodríguez,

Bonfrate,

Park

et al. 2023

J. Phys. Chem. A

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“…42 The doubles are critical components for the accurate descriptions of excited states, bond breakings, conical intersections, etc., which significantly expands the applicability of MRSF-TDDFT. (6) Recently, it has been demonstrated that the high spin triplet reference of MRSF-TDDFT provides a simple way of ensuring core-hole relaxation for accurate XAS (X-ray absorption), 43 which has been one of the main difficulties of LR-TDDFT. Detailed discussions can be found later in the main text.…”

mentioning

confidence: 99%

“…In the case of LR-TDDFT, the corresponding accuracy is crude, with errors as large as ∼10 eV for second-period elements like C, N, O, and F, and even larger errors for heavier elements. With the additional scalar relativistic effects on K-edge excitation energies of 24 s- and 17 third-row molecules, on the other hand, the particular ΔCHP-MRSF(R) exhibited near-perfect predictions with root-mean-square error (RMSE) ≈ 0.5 eV, featuring a median of 0.3 and an interquartile range of 0.4 . The XAS of valence excited states can also be calculated by the same protocol.…”

mentioning

confidence: 99%

“…The XAS of valence excited states can also be calculated by the same protocol. The 1 s core excitation spectra of oxygens either of ππ * (π hole) and nπ * ( n hole) states of the three particular structures (FC, CI 21 , and S 1 min) of thymine were simulated by ΔCHP-MRSF(R), and the results are presented in Figure b . Remarkably, a near perfect 1 s ( O 8) → n ( O 8) core to valence n hole excitation value of 526.8 eV (exp.…”

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confidence: 99%

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Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory: Multireference Advantages with the Practicality of Linear Response Theory

Park,

Komarov,

Lee

et al. 2023

J. Phys. Chem. Lett.

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The density functional theory (DFT) and linear response (LR) time-dependent (TD)-DFT are of the utmost importance for routine computations. However, the single reference formulation of DFT suffers in the description of open-shell singlet systems such as diradicals and bond-breaking. LR-TDDFT, on the other hand, finds difficulties in the modeling of conical intersections, doubly excited states, and core-level excitations. In this Perspective, we demonstrate that many of these limitations can be overcome by recently developed mixed-reference (MR) spin-flip (SF)-TDDFT, providing an alternative yet accurate route for such challenging situations. Empowered by the practicality of the LR formalism, it is anticipated that MRSF-TDDFT can become one of the major workhorses for general routine tasks.

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Advanced quantum and semiclassical methods for simulating photoinduced molecular dynamics and spectroscopy

Faraji,

Picconi,

Palacino‐González

2024

WIREs Comput Mol Sci

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Molecular‐level understanding of photoinduced processes is critically important for breakthroughs in transformative technologies utilizing light, ranging from photomedicine to photoresponsive materials. Theory and simulation play a crucial role in this task. Despite great advances in hardware and computational methods, the theoretical description of photoinduced phenomena in the presence of complex environments and external photoexcitation conditions still poses formidable challenges for theoreticians and there are numerous formal and computational difficulties that must be overcome. The development of predictive, accurate, and at the same time, computationally efficient theoretical approaches to describe complex problems in photochemistry and photophysics is an active field of research in contemporary theoretical and computational chemistry. In this advanced review, we discuss modern computational advances and novel approaches that have been recently developed in excited‐electronic structure methods, and multiscale modeling, with a special emphasis on coupled electron‐nuclear dynamics and spectroscopy, from fully quantum to semi‐classical methodologies—including dissipative effects, the explicit light field interaction, femtosecond time‐resolved spectroscopy, and software infrastructure.This article is categorized under: Software > Quantum Chemistry Electronic Structure Theory > Combined QM/MM Methods Theoretical and Physical Chemistry > Spectroscopy Software > Molecular Modeling

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Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory for Accurate X-ray Absorption Spectroscopy

Cited by 15 publications

References 77 publications

Solvent Effects and pH Dependence of the X-ray Absorption Spectra of Proline from Electrostatic Embedding Quantum Mechanics/Molecular Mechanics and Mixed-Reference Spin-Flip Time-dependent Density-Functional Theory

Solvent Effects and pH Dependence of the X-ray Absorption Spectra of Proline from Electrostatic Embedding Quantum Mechanics/Molecular Mechanics and Mixed-Reference Spin-Flip Time-dependent Density-Functional Theory

Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory: Multireference Advantages with the Practicality of Linear Response Theory

Advanced quantum and semiclassical methods for simulating photoinduced molecular dynamics and spectroscopy

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