TURBOMOLE: Today and Tomorrow

Journal of Chemical Theory and Computation, Journal Year: 2023, Volume and Issue: 19(20), P. 6859 - 6890

Published: June 29, 2023

TURBOMOLE is a highly optimized software suite for large-scale quantum-chemical and materials science simulations of molecules, clusters, extended systems, periodic solids. uses Gaussian basis sets has been designed with robust fast applications in mind, ranging from homogeneous heterogeneous catalysis to inorganic organic chemistry various types spectroscopy, light-matter interactions, biochemistry. This Perspective briefly surveys TURBOMOLE's functionality highlights recent developments that have taken place between 2020 2023, comprising new electronic structure methods molecules solids, previously unavailable molecular properties, embedding, dynamics approaches. Select features under development are reviewed illustrate the continuous growth program suite, including nuclear orbital methods, Hartree-Fock-based adiabatic connection models, simplified time-dependent density functional theory, relativistic effects magnetic multiscale modeling optical properties.

Language: Английский

---

Application of the noncollinear Scalmani–Frisch formalism to current density functional theory

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(8)

Published: Feb. 25, 2025

We generalize the noncollinear formalism proposed by Scalmani and Frisch [J. Chem. Theory Comput. 8, 2193 (2012)] to include particle spin current densities for meta-generalized gradient approximations local hybrid functionals. This allows us fully impact of spin–orbit coupling in relativistic calculations applications finite magnetic fields. For latter, we use London atomic orbitals ensure gauge origin invariance. It is shown that this superior more common canonical approach calculations, as it naturally includes all three closed-shell limit avoids projection onto magnetization vector. important easily restore rotational invariance limit. In addition, Scalmani–Frisch can be made numerically stable may lead a nonvanishing torque. However, both formalisms are rotationally invariant open-shell systems

Language: Английский

---

Beyond Explored Functionals: A Computational Journey of Two-Photon Absorption

Journal of Chemical Theory and Computation, Journal Year: 2024, Volume and Issue: 20(9), P. 3879 - 3893

Published: April 22, 2024

We present a thorough investigation into the efficacy of 19 density functional theory (DFT) functionals, relative to RI-CC2 results, for computing two-photon absorption (2PA) cross sections (σ2PA) and key dipole moments (|μ00|, |μ11|, |Δμ|, |μ01|) series coumarin dyes in gas-phase. The functionals include different categories, including local approximation (LDA), generalized gradient (GGA), hybrid-GGA (H-GGA), range-separated (RSH-GGA), meta-GGA (M-GGA), hybrid M-GGA (HM-GGA), with 14 them being subjected analysis first time respect predicting σ2PA values. Analysis reveals that integrating both short-range (SR) long-range (LR) corrections, particularly those within RSH-GGA HM-GGA classes, outperform others. Furthermore, range-separation approach was found more impactful compared varying percentages Hartree–Fock exchange (HF Ex) functionals. traditionally recommended 2PA do not appear among top 9 our study, which is interesting, as these top-performing have been previously investigated this context. This list dominated by M11, QTP variants, ωB97X, ωB97X-V, M06-2X, surpassing performance other commonly used CAM-B3LYP.

Language: Английский

---

Comment on: “Toward Accurate Two-Photon Absorption Spectrum Simulations: Exploring the Landscape beyond the Generalized Gradient Approximation”

The Journal of Physical Chemistry Letters, Journal Year: 2024, Volume and Issue: 15(23), P. 6237 - 6240

Published: June 13, 2024

A recent benchmark study of two-photon absorption (2PA) strengths using meta-generalized gradient approximation (MGGA) exchange-correlation functionals by Ahmadzadeh, Li, Rinkevicius, Norman, and Zaleśny (ALRNZ24) [

Language: Английский

---

Reference CC3 Excitation Energies for Organic Chromophores: Benchmarking TD-DFT, BSE/GW, and Wave Function Methods

Journal of Chemical Theory and Computation, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 5, 2024

To expand the QUEST database of highly accurate vertical transition energies, we consider a series large organic chromogens ubiquitous in dye chemistry, such as anthraquinone, azobenzene, BODIPY, and naphthalimide. We compute, at CC3 level theory, singlet triplet energies associated with low-lying excited states. This leads to collection more than 120 new excitation energies. For several transitions, have been able determine CCSDT compact basis set, finding minimal deviations from values for most Subsequently, employ these reference benchmark lower-order wave function approaches, including popular ADC(2) CC2 schemes, well time-dependent density-functional theory (TD-DFT), both without applying Tamm-Dancoff approximation (TDA). At TD-DFT level, evaluate panel global, range-separated, local, double hybrid functionals. Additionally, assess performance Bethe-Salpeter equation (BSE) formalism relying on G0W0 evGW quasiparticle evaluated various starting points. It turns out that ADC(2.5) are models among those respective O(N5) O(N6) scalings system size. In contrast, CCSD does not outperform CC2. The best performing exchange-correlation functionals include BMK, M06-2X, M06-SX, CAM-B3LYP, ωB97X-D, LH20t, average approximately 0.20 eV or slightly below. Errors can be further reduced by considering hybrids. Both SOS-ωB88PP86 SOS-ωPBEPP86 exhibit particularly attractive performances overall quality par CC2, whereas PBE0-DH PBE-QIDH only less efficient. BSE/evGW calculations based Kohn-Sham points found effective but much their counterparts.

Language: Английский

---

Computational insights into two-photon absorption of centrosymmetric organoboron complexes

Chemical Physics Letters, Journal Year: 2025, Volume and Issue: unknown, P. 141907 - 141907

Published: Jan. 1, 2025

Language: Английский

---

Simulations of Two-Photon Absorption Spectra of Fluorescent Dyes: The Impact of Non-Condon Effects

Journal of Chemical Theory and Computation, Journal Year: 2025, Volume and Issue: unknown

Published: March 26, 2025

Computer simulations play a pivotal role in interpreting experimental two-photon absorption (2PA) spectra. One of the key aspects simulation these spectra is to take into account vibrational fine structure bands electronic This typically done by employing Franck–Condon (FC) term and low-order terms Herzberg–Teller (HT) expansion. In this work, we present systematic study first-order HT effects on vibronic π → π* 2PA 13 common fluorophores. We begin evaluating performance several density functional approximations (DFAs) against second-order coupled cluster singles doubles model (CC2) for reproducing transition moments their first- derivatives with respect normal modes vibration set six donor–acceptor molecules. Our findings reveal that most DFAs produce inaccurate values derivatives, exception LC-BLYP functionals range–separation parameters 0.33 0.47. Although underestimate contribution total intensities bands, they offer reasonable qualitative reproduction reference further explore fluorescent chromophores, finding contributions are secondary FC effects, leading small shifts wavelengths peaks, minimal changes intensities. Additionally, adiabatic Hessian, vertical gradient models assessed. The general agreement among confirms harmonic approximation suitable studying selected

Language: Английский

---

Two-Photon Absorption Strengths of Small Molecules: Reference CC3 Values and Benchmarks

Journal of Chemical Theory and Computation, Journal Year: 2024, Volume and Issue: 20(20), P. 9093 - 9106

Published: Oct. 7, 2024

We present a large dataset of highly accurate two-photon transition strengths (δTPA) determined for standard small molecules. Our reference values have been calculated using the quadratic response implementation third-order coupled cluster method including iterative triples (Q-CC3). The aug-cc-pVTZ atomic basis set is used molecules with up to five non-hydrogen atoms, while larger are assessed aug-cc-pVDZ; differences due sets discussed. This dataset, encompassing 82 singlet transitions various characters (Rydberg, valence, and double excitations), enables comprehensive benchmark smaller alternative wavefunction methods when Q-CC3 calculations become beyond reach as well time-dependent density functional theory (TD-DFT) approaches. evaluated include equation-of-motion CCSD approximations, Q-CC2, second-order algebraic diagrammatic construction in its intermediate state representation (I-ADC2). In TD-DFT framework, commonly exchange–correlation functionals evaluted. extensive analysis provides quantitative assessment these methods, revealing how different system sizes, intensities, types affect their performances.

Language: Английский

---

A General and Transferable Local Hybrid Functional for Electronic Structure Theory and Many-Fermion Approaches

Journal of Chemical Theory and Computation, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 20, 2024

Density functional theory has become the workhorse of quantum physics, chemistry, and materials science. Within these fields, a broad range applications needs to be covered. These from solids molecular systems, organic inorganic or even electrons other Fermions, such as protons muons. This is emphasized by plethora density approximations that have been developed for various cases. In this work, two new local hybrid exchange-correlation functionals are constructed first-principles, promoting generality transferability. We show constraint satisfaction can achieved admixtures with full exact exchange, without sacrificing accuracy. The performance CHYF-PBE CHYF-B95 assessed thermochemical properties, excitation energies, Mössbauer isomer shifts, NMR spin-spin coupling constants, shieldings magnetizabilities, EPR hyperfine constants. Here, shows excellent throughout all tests numerically robust only requiring small grids converged results. Additionally, both easily generalized arbitrary Fermions shown electron-proton correlation energies. Therefore, we outline generated in way general purpose tools mechanical studies.

Language: Английский

---

Beyond Explored Functionals: A Computational Journey of Two-Photon Absorption

Published: Jan. 31, 2024

We present a thorough investigation into the efficacy of 19 DFT functionals, relative to RI-CC2 results, for computing two-photon absorption (2PA) cross-sections (σ2PA) and key dipole moments (µ00, µ11, Δµ, µ01) series coumarin dyes in gas-phase. The functionals include different categories, including local density approximation (LDA), generalized gradient (GGA), hybrid-GGA (H-GGA), range separated (RSH-GGA), meta-GGA (M-GGA), hybrid M-GGA (HM-GGA), with 14 them being subjected analysis first time respect predicting σ2PA values. Analysis reveals that integrating both short-range (SR) long-range (LR) corrections, particularly those within RSH GGA HM-GGA classes, outperform others. Furthermore, range-separation approach was found more impactful compared varying percentages Hartree-Fock exchange (HF Ex) functionals. traditionally recommended 2PA do not appear among top 9 our study, which is interesting as these top-performing have been previously investigated this context. This list dominated by M11, QTP variants, ωB97X, ωB97X-V, M06-2X, surpassing performance other commonly used CAM-B3LYP.

Language: Английский

---