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This study investigates the impact of structural isomerism on the excited state lifetime and redox energetics of heteroleptic [Ir(ppy)2(bpy)]+ and homoleptic Ir(ppy)3 photoredox catalysts using ground-state and time-dependent density functional theory methods. While the ground- and excited-state reduction potentials differ only slightly among the isomers of these complexes, our findings reveal significant variations in the radiative and non-radiative decay rates of the reactivity-controlling triplet 3MLCT states of these closely related species. The observed differences in radiative decay rates could be traced back to variations in the transition dipole moment, vertical energy gaps, and spin–orbit coupling of the isomers. In [Ir(ppy)2(bpy)]+, transition dipole moment differences play a significant role in controlling the relative lifetime of the triplet states, which we rationalized by a vectorial analysis of permanent dipole moments of the ground and excited states. Regarding the two isomers of Ir(ppy)3, changes in radiative decay rates were primarily attributed to variations in vertical energy gaps and intensity borrowing from other singlet-singlet transitions driven by spin–orbit coupling. Non-radiative decay variations were assessed in terms of differences in reorganization energies, adiabatic energy gap, and spin–orbit coupling. For both complexes, reorganization energies associated with low-energy molecular vibrations and metal–ligand bond length changes following the de-excitation process were major contributors. These insights provide a deeper understanding of how molecular design can be leveraged to optimize the performance of iridium-based photoredox catalysts, potentially guiding the development of more efficient catalytic systems for future applications. [ABSTRACT FROM AUTHOR]

In this paper, we demonstrate the performance of several density-based methods in predicting the inversion of S1 and T1 states of a few N-heterocyclic triangulene based fused ring molecules (popularly known as INVEST molecules) with an eye to identify a well performing but cost-effective preliminary screening method. Both conventional linear-response time-dependent density functional theory (LR-TDDFT) and ΔSCF methods (namely maximum overlap method, square-gradient minimization method, and restricted open-shell Kohn–Sham) are considered for excited state computations using exchange–correlation (XC) functionals from different rungs of Jacob's ladder. A well-justified systematism is observed in the performance of the functionals when compared against fully internally contracted multireference configuration interaction singles and doubles and/or equation of motion coupled-cluster singles and doubles (EOM-CCSD), with the most important feature being the capture of spin-polarization in the presence of correlation. A set of functionals with the least mean absolute error is proposed for both the approaches, LR-TDDFT and ΔSCF, which can be more cost-effective alternatives for computations on synthesizable larger derivatives of the templates studied here. We have based our findings on extensive studies of three cyclazine-based molecular templates, with additional studies on a set of six related templates. Previous benchmark studies for subsets of the functionals were conducted against the domain-based local pair natural orbital-similarity transformed EOM-CCSD (STEOM-CCSD), which resulted in an inadequate evaluation due to deficiencies in the benchmark theory. The role of exact-exchange, spin-contamination, and spin-polarization in the context of DFT comes to the forefront in our studies and supports the numerical evaluation of XC functionals for these applications. Suitable connections are drawn to two and three state exciton models, which identify the minimal physics governing the interactions in these molecules. [ABSTRACT FROM AUTHOR]

This study investigates the impact of structural isomerism on the excited state lifetime and redox energetics of heteroleptic [Ir(ppy)2(bpy)]+ and homoleptic Ir(ppy)3 photoredox catalysts using ground-state and time-dependent density functional theory methods. While the ground- and excited-state reduction potentials differ only slightly among the isomers of these complexes, our findings reveal significant variations in the radiative and non-radiative decay rates of the reactivity-controlling triplet 3MLCT states of these closely related species. The observed differences in radiative decay rates could be traced back to variations in the transition dipole moment, vertical energy gaps, and spin–orbit coupling of the isomers. In [Ir(ppy)2(bpy)]+, transition dipole moment differences play a significant role in controlling the relative lifetime of the triplet states, which we rationalized by a vectorial analysis of permanent dipole moments of the ground and excited states. Regarding the two isomers of Ir(ppy)3, changes in radiative decay rates were primarily attributed to variations in vertical energy gaps and intensity borrowing from other singlet-singlet transitions driven by spin–orbit coupling. Non-radiative decay variations were assessed in terms of differences in reorganization energies, adiabatic energy gap, and spin–orbit coupling. For both complexes, reorganization energies associated with low-energy molecular vibrations and metal–ligand bond length changes following the de-excitation process were major contributors. These insights provide a deeper understanding of how molecular design can be leveraged to optimize the performance of iridium-based photoredox catalysts, potentially guiding the development of more efficient catalytic systems for future applications. [ABSTRACT FROM AUTHOR]

Silicon carbide (SiC) exhibits superior properties, including a wide bandgap, high breakdown electric field, high thermal conductivity, high electron saturation drift velocity, strong radiation resistance, and excellent chemical stability, making it highly suitable for power device applications. In the substrate slicing process for fabricating SiC power devices, pulsed laser technology provides several advantages over traditional diamond wire sawing, including a smaller heat-affected zone, reduced thermal defects, higher precision, and improved efficiency. To gain a deeper understanding of the interaction between femtosecond lasers and 4H-SiC materials at the atomic scale, this study employs real-time time-dependent density functional theory simulations, incorporating carrier cooling to maintain detailed balance. The analysis examines the evolution of carrier number, density of states, Si–C bond length, and atomic disorder over time under photoexcitation at varying wavelengths and intensities. The results indicate that ultrafast non-thermal melting in 4H-SiC arises from carrier localization, which induces uneven interatomic forces, leading to local atomic displacements, which increases atomic bond lengths and ultimately results in melting. Long-wavelength 1064 nm laser irradiation was found to cause greater atomic force imbalances and displacements than shorter wavelengths (266 and 532 nm), leading to more pronounced non-thermal melting. This study provides atomic-scale theoretical support for research on femtosecond laser processing of 4H-SiC ingots and substrates. [ABSTRACT FROM AUTHOR]

The formalism to calculate excited state properties from the GW–Bethe–Salpeter equation (BSE) method is introduced, providing convenient access to excited state absorption, excited state circular dichroism, and excited state optical rotation in the framework of the GW–BSE method. This is achieved using the second-order transition density, which can be obtained by solving a set of auxiliary equations similar to time-dependent density functional theory (TD-DFT). The proposed formulation therefore leads to no increase in the formal computational complexity when compared to the corresponding ground state properties. We further outline the calculation of fully relaxed spin–orbit coupling matrix elements within the GW–BSE method, allowing us to include perturbative corrections for spin–orbit coupling in aforementioned properties. These corrections are also extended to TD-DFT. Excited state absorption and perturbative spin–orbit coupling corrections within GW–BSE are evaluated for a selected set of molecular systems, yielding promising results. [ABSTRACT FROM AUTHOR]

Time-dependent density functional theory was employed to investigate the electron dynamics of MoS2 following femtosecond pulse irradiation. The study concerned the effects of laser wavelength, intensities, and polarization and elucidated the ionization mechanisms across the intensity range of 1010–1014 W/cm2. As laser intensity increases, MoS2 irradiated with an infrared (IR) laser (800 nm) deviates from single-photon absorption at lower intensities compared to that subjected to an ultraviolet (UV) laser (266 nm), and nonlinear effects in the current arise at lower intensities for the 800 nm laser. At a wavelength of 266 nm, MoS2 irradiated with an a-axis polarized laser deposited more energy and generated more electron–hole pairs compared to c-axis polarization. Rate equations were used to estimate the total number of excited electrons in MoS2 and the corresponding plasma frequency. Simulation results indicate that the damage threshold of the UV laser is higher than that of the IR laser, which contradicts the experimental results. This outcome suggests that the mechanism of material damage induced by the UV femtosecond laser near the damage threshold is independent of optical breakdown. The findings of this research are significant for enhancing the performance of MoS2-based photodetectors and optimizing their stability and reliability in high-power, short-wavelength laser applications. [ABSTRACT FROM AUTHOR]

Singlet fission (SF) is a charge carrier multiplication process that has potential for improving the performance of (opto)electronic devices from the conversion of one singlet exciton S1 into two triplet excitons T1 via a spin-entangled triplet pair state 1(TT). This process depends highly on molecular packing and morphology, both for the generation and dissociation of 1(TT) states. Many benchmark SF materials, such as acenes, are also prone to photodegradation reactions, such as endoperoxide (EPO) formation and photodimerization, which inhibit realization of SF devices. In this paper, we compare functionalized tetracenes R–Tc with two packing motifs: "slip-stack" packing in R = TES, TMS, and tBu and "gamma" packing in R = TBDMS to determine the effects of morphology on SF as well as on photodegradation using a combination of temperature and magnetic field dependent spectroscopy, kinetic modeling, and time-dependent density functional theory. We find that both "slip-stack" and "gamma" packing support SF with high T1 yield at room temperature (up to 191% and 181%, respectively), but "slip-stack" is considerably more advantageous at low temperatures (< 150 K). In addition, each packing structure has a distinct emissive relaxation pathway competitive to SF, while the states involved in the SF itself are dark. The "gamma" packing has superior photostability, both in regards to EPO formation and photodimerization. The results indicate that the trade-off between SF efficiency and photostability can be overcome with material design, emphasize the importance of considering both photophysical and photochemical properties, and inform efforts to develop optimal SF materials for (opto)electronic applications. [ABSTRACT FROM AUTHOR]

We present a Lagrangian-based implementation of Ehrenfest dynamics with nuclear–electronic orbital (NEO) theory and real-time time-dependent density functional theory for extended periodic systems. In addition to a quantum dynamical treatment of electrons and selected protons, this approach allows for the classical movement of all other nuclei to be taken into account in simulations of condensed matter systems. Furthermore, we introduce a Lagrangian formulation for the traveling proton basis approach and propose new schemes to enhance its application for extended periodic systems. Validation and proof-of-principle applications are performed on electronically excited proton transfer in the o-hydroxybenzaldehyde molecule with explicit solvating water molecules. These simulations demonstrate the importance of solvation dynamics and a quantum treatment of transferring protons. This work broadens the applicability of the NEO Ehrenfest dynamics approach for studying complex heterogeneous systems in the condensed phase. [ABSTRACT FROM AUTHOR]

The collision of cesium atoms on the surface of helium nanodroplets (HNDs) containing 1000 atoms is described by the ZPAD-mPL approach, a zero-point averaged dynamics (ZPAD) method based on a He–He pseudopotential adjusted to better reproduce the total energy of He1000. Four types of collisional patterns were identified depending on the initial projectile speed v0 and impact parameter b. At the lowest speeds (v0 ≲ 250 m s−1), Cs atoms are softly captured by the HND surface, while at the highest ones (v0 ≳ 500–600 m s−1), Cs atoms can travel through the droplet and move away. In between these two extreme cases, Cs atoms can be temporarily submerged in the HND before being expelled to the surface if b = 0 or cross the HND before being captured on its surface. The possibility for Cs capture at experimental velocities and droplet piercings at the highest ones contrasts with time-dependent density functional theory calculations, which predict Cs capture for velocities lower than 75 m s−1, and ring-polymer molecular dynamics (RPMD) or former ZPAD-like methods, which predict soft Cs capture up to 500 m s−1. ZPAD-mPL results are attributed to the liquid but non-superfluid nature of the droplet, which favors energy exchanges with the helium environment, and to low He–He binding energy and HND surface tension, which can stimulate helium ejections, especially at high projectile speeds. Despite the use of a pseudopotential to model He–He interactions, the heliophobicity of Cs atoms is maintained as demonstrated by their ability to remain localized on the HND surface or to be expelled to the HND surface after transient submersion in helium. [ABSTRACT FROM AUTHOR]

We introduce an individually fitted screened-exchange interaction for the time-dependent Hartree–Fock (TDHF) method and show that it resolves the missing binding energies in polymethine organic dye molecules compared to time-dependent density functional theory (TDDFT). The interaction kernel, which can be thought of as a dielectric function, is generated by stochastic fitting to the screened-Coulomb interaction of many-body perturbation theory (MBPT), specific to each system. We test our method on the flavylium and indocyanine green dye families with a modifiable length of the polymethine bridge, leading to excitations ranging from visible to short-wave infrared. Our approach validates earlier observations on the importance of inclusion of medium range exchange for the exciton binding energy. Our resulting method, TDHF@vW, also achieves a mean absolute error on a par with MBPT at a computational cost on a par with local-functional TDDFT. [ABSTRACT FROM AUTHOR]

Optical trapping is an effective tool for manipulating micrometer-sized particles, although its application to nanometer-sized particles remains difficult. The field of optical trapping has advanced significantly, incorporating more advanced techniques such as plasmonic structures. However, single-molecule trapping remains a challenge. To achieve a deeper understanding of optical forces acting on molecular systems, a first-principles approach to analyze the optical force on molecules interacting with a plasmonic field is crucial. In our study, the optical force and torque induced by the near-field excitation of C3H6 were investigated using real-time time-dependent density functional theory calculations on real-space grids. The near field from the scanning tunneling probe was adopted as the excitation source for the molecule. The optical force was calculated using the polarization charges induced in the molecule based on Lorentz force. While the optical force and torque calculated as functions of the light energy were in moderate agreement with the oscillator strengths obtained from the far-field excitation of C3H6, a closer correspondence was achieved with the power spectrum of the induced dipole moment using near-field excitation. Time-domain analysis of the optical force suggests that the simultaneous excitation of multiple excited states generally weakens the force because of mismatches between the directions of the induced polarization and the electric field. This study revealed a subtle damping mechanism for the optical force arising from intrinsic electronic states and the influence of beating. [ABSTRACT FROM AUTHOR]

When using quantum chemical methods to study electronically excited states of open-shell molecules, it is often beneficial to start with wave functions that are spin eigenfunctions. For excited states of molecules containing heavy elements, spin–orbit coupling (SOC) is important and needs to be included as well. An efficient approach is to include SOC perturbatively on top of a restricted open-shell Kohn–Sham (ROKS) time-dependent density functional theory, which can be combined with the Tamm–Dancoff approximation (TDA) to suppress numerical instabilities. We implemented and assessed the potential of such a ROKS-TDA-SOC method, also featuring the possibility of calculating transition dipole moments between states to allow for full spectrum simulation. Our study shows that the ROKS-TDA-SOC formalism yields a clear and easy-to-use method to obtain electronically excited states of open-shell molecules that are of moderate size and contain heavy elements. [ABSTRACT FROM AUTHOR]

This study provides accurate results for the electronic stopping cross sections of H, He, N, and Ne in silicon in low to intermediate energy ranges using various non-perturbative theoretical methods, including real-time time-dependent density functional theory, transport cross section, and induced-density approach. Recent experimental findings [Ntemou et al., Phys. Rev. B 107, 155145 (2023)] revealed discrepancies between the estimates of density functional theory and the observed values. We show that these discrepancies vanish by considering the nonuniform electron density of the deeper silicon bands for ion velocities approaching zero (v → 0). This indicates that mechanisms such as "elevator" and "promotion," which can dynamically excite deeper-band electrons, are active, enabling a localized free-electron gas to emulate ion energy loss, as pointed out by Lim et al. [Phys. Rev. Lett. 116, 043201 (2016)]. The observation and the description of a velocity-proportionality breakdown in electronic stopping cross sections at very low velocities are considered to be a signature of the contributions of deeper-band electrons. [ABSTRACT FROM AUTHOR]

Electron dynamics of the Na10 chain and the Na10–N2 complex locally excited by an atomistic optical near-field are investigated using real-time time-dependent density functional theory calculations on real-space grids. Ultrafast laser pulses were used to simulate the near-field excitation under on- and off-resonance conditions. Off-resonance excitation did not lead to the propagation of the excitation through the Na10 chain. In contrast, under the resonance conditions, the excited state is delocalized over the entire Na chain. Analysis of the local dipole moment of each atom in Na10 indicates that this behavior is consistent with the transition density. Adding an N2 molecule to the opposite end of the local excitation region results in energy transfer via the Na10 chain. The energy transfer efficiency of the N2 molecule is well correlated with the absorption spectrum of Na10. The present study paves the way for realizing remote excitation and photonic devices at the atomic scale. [ABSTRACT FROM AUTHOR]

The isomerization of azobenzo-13-crown ether can be expected to be hindered due to the polyoxyethylene linkage connecting the 2,2′-positions of azobenzene. The mixed reference spin-flip time-dependent density functional theory results reveal that the planar and rotational minima of the first photo-excited singlet state (S1) of the trans-isomer pass through a barrier (2.5–5.0 kcal/mol) as it goes toward the torsional conical intersection (S0/S1) geometry (

We simulate the photodynamics of gas-phase cyclobutanone excited to the S2 state using fewest switches surface hopping (FSSH) dynamics powered by time-dependent density functional theory (TDDFT). We predict a total photoproduct yield of 8%, with a C3:C2 product ratio of 0 trajectories to 8 trajectories. One primary S2 → S1 conical intersection is identified involving the compression of an α-carbon–carbon–hydrogen bond angle. Excited state lifetimes computed with respect to electronic state populations were found to be 3.96 ps (S2 → S1) and 498 fs (S1 → S0). We also generate time-resolved difference pair distribution functions (ΔPDFs) from our TDDFT-FSSH dynamics results in order to generate direct comparisons with ultrafast electron diffraction experiment observables. Global and target analysis of time-resolved ΔPDFs produced a distinct set of lifetimes: (i) a 0.548 ps decay and (ii) a 1.69 ps decay, both resembling the S2 minimum, as well as (iii) a long decay that resembles the S1 minimum geometry and the fully separated C2 products. Finally, we contextualize our results by considering the impact of the most likely sources of significant errors. [ABSTRACT FROM AUTHOR]

The efficient and stable electroluminescence of quantum dots (QDs) is of great importance in their applications in new display technologies. The short service life of blue QDs, however, hinders their development and commercialization. Different mechanisms have been proposed for the destabilization of QDs in electroluminescent processes. Based on real-time time-dependent density functional theory studies on the QD models covered by Z-type ligands (XAc2, X = Cd, Zn, Mg), the structural evolution is simulated to reveal the mechanism of the reduction reactions induced by electron injection. Our simulations reproduce the experimental observations that the reduction reactions occur at the QD–ligand interface, and the reduced Cd atom is almost in a zero valence state. However, different sites are predicted for the reactions in which the surface metal atom of the QD instead of the metal atom in the ligands is reduced. As a result, one of the arms of the chelate ligand leaves the QD, which tends to cause damage to its electroluminescent performance. Our findings contribute to a mechanistic understanding of the reduction reactions that occurred at the QD–ligand interface. [ABSTRACT FROM AUTHOR]

The plane-wave pseudopotential (PW-PP) formalism is widely used for the first-principles electronic structure calculation of extended periodic systems. The PW-PP approach has also been adapted for real-time time-dependent density functional theory (RT-TDDFT) to investigate time-dependent electronic dynamical phenomena. In this work, we detail recent advances in the PW-PP formalism for RT-TDDFT, particularly how maximally localized Wannier functions (MLWFs) are used to accelerate simulations using the exact exchange. We also discuss several related developments, including an anti-Hermitian correction for the time-dependent MLWFs (TD-MLWFs) when a time-dependent electric field is applied, the refinement procedure for TD-MLWFs, comparison of the velocity and length gauge approaches for applying an electric field, and elimination of long-range electrostatic interaction, as well as usage of a complex absorbing potential for modeling isolated systems when using the PW-PP formalism. [ABSTRACT FROM AUTHOR]

In this work, we have implemented the time-dependent density functional theory approximate auxiliary s function (TDDFT-aas) method, which is an approximate TDDFT method. Instead of calculating the exact two-center electron integrals in the K coupling matrix when solving the Casida equation, we approximate the integrals, thereby reducing the computational cost. In contrast to the related TDDFT plus tight-binding (TDDFT+TB) method, a new type of gamma function is used in the coupling matrix that does not depend on the tight-binding parameters. The calculated absorption spectra of silver and gold nanoparticles using TDDFT-aas show good agreement with TDDFT and TDDFT+TB results. In addition, we have implemented the analytical excited-state gradients for the TDDFT-aas method, which makes it possible to calculate the emission energy of molecular systems. [ABSTRACT FROM AUTHOR]

This study explores various models of semiconductor dielectric functions, with a specific emphasis on the large wavenumber spectrum and the derivation of the screened exchange interaction. Particularly, we discuss the short-range effect of the screened exchange potential. Our investigation reveals that the short-range effect originating from the high wavenumber spectrum is contingent upon the dielectric constant of the targeted system. To incorporate dielectric-dependent behaviors concerning the short-range aspect into the dielectric density functional theory (DFT) framework, we utilize the local Slater term and the Yukawa-type term, adjusting the ratio between these terms based on the dielectric constant. Additionally, we demonstrate the efficacy of the time-dependent dielectric DFT method in accurately characterizing the electronic structure of excited states in dyes and functional molecules. Several theoretical approaches have incorporated parameters dependent on the system to elucidate short-range exchange interactions. Our theoretical analysis and discussions will be useful for those studies. [ABSTRACT FROM AUTHOR]

Endohedrally doped clusters form a large category of cage clusters, with unique structures, diverse elemental compositions, and highly tunable electronic structures and physisochemical properties. They have been widely achieved in laboratory and may serve as functional building blocks for assembling new supermolecular structures and devices. In this paper, for the first time, we disclosed the luminescence properties of endohedrally doped group-IV clusters by time-dependent density functional theory calculations. A total of 64 cage clusters have been explored in terms of stability, emission wavelength, and the energy difference between the first excited singlet and triplet states. The key geometric and electronic factors governing the photophysical properties of these cage clusters were unveiled, to provide crucial insights for crafting atomically precise nanoclusters for optical and optoelectronic applications. [ABSTRACT FROM AUTHOR]

We investigate the performance of time-dependent density functional theory (TDDFT) for reproducing high-level reference x-ray absorption spectra of liquid water and water clusters. For this, we apply the integrated absolute difference (IAD) metric, previously used for x-ray emission spectra of liquid water [T. Fransson and L. G. M. Pettersson, J. Chem. Theory Comput. 19, 7333–7342 (2023)], in order to investigate which exchange–correlation (xc) functionals yield TDDFT spectra in best agreement to reference, as well as to investigate the suitability of IAD for x-ray absorption spectroscopy spectrum calculations. Considering highly asymmetric and symmetric six-molecule clusters, it is seen that long-range corrected xc-functionals are required to yield good agreement with the reference coupled cluster (CC) and algebraic-diagrammatic construction spectra, with 100% asymptotic Hartree–Fock exchange resulting in the lowest IADs. The xc-functionals with best agreement to reference have been adopted for larger water clusters, yielding results in line with recently published CC theory, but which still show some discrepancies in the relative intensity of the features compared to experiment. [ABSTRACT FROM AUTHOR]

Localization procedures are an important tool for analysis of complex systems in quantum chemistry, since canonical molecular orbitals are delocalized and can, therefore, be difficult to align with chemical intuition and obscure information at the local level of the system. This especially applies to calculations obeying periodic boundary conditions. The most commonly used approach to localization is Foster–Boys Wannier functions, which use a unitary transformation to jointly minimize the second moment of the orbitals. This procedure has proven to be robust and fast but has a side effect of often mixing σ - and π -type orbitals. σ / π -separation is achieved by the Pipek–Mezey Wannier function (PMWF) approach [Lehtola and Jónsson, J. Chem. Theory Comput. 10, 642 (2014) and Jónsson et al., J. Chem. Theory Comput. 13, 460 (2017)], which defines the spread functional in terms of partial charges instead. We have implemented a PMWF algorithm in the CP2K software package using the Cardoso–Souloumiac algorithm to enable their application to real-time time-dependent density functional theory. The method is demonstrated on stacked CO 2 molecules, linear acetylenic carbon, boron and nitrogen co-doped graphene, and nitrogen-vacancy doped diamond. Finally, we discuss its computational scaling and recent efforts to improve it with fragment approaches. [ABSTRACT FROM AUTHOR]

Computational modeling of plasmon-mediated molecular photophysical and photochemical behaviors can help us better understand and tune the bound molecular properties and reactivity and make better decisions to design and control nanostructures. However, computational investigations of coupled plasmon–molecule systems are challenging due to the lack of accurate and efficient protocols to simulate these systems. Here, we present a hybrid scheme by combining the real-time time-dependent density functional theory (RT-TDDFT) approach with the time-domain frequency dependent fluctuating charge (TD-ωFQ) model. At first, we transform ωFQ in the frequency-domain, an atomistic electromagnetic model for the plasmonic response of plasmonic metal nanoparticles (PMNPs), into the time-domain and derive its equation-of-motion formulation. The TD-ωFQ introduces the nonequilibrium plasmonic response of PMNPs and atomistic interactions to the electronic excitation of the quantum mechanical (QM) region. Then, we combine TD-ωFQ with RT-TDDFT. The derived RT-TDDFT/TD-ωFQ scheme allows us to effectively simulate the plasmon-mediated "real-time" electronic dynamics and even the coupled electron–nuclear dynamics by combining them with the nuclear dynamics approaches. As a first application of the RT-TDDFT/TD-ωFQ method, we study the nonradiative decay rate and plasmon-enhanced absorption spectra of two small molecules in the proximity of sodium MNPs. Thanks to the atomistic nature of the ωFQ model, the edge effect of MNP on absorption enhancement has also been investigated and unveiled. [ABSTRACT FROM AUTHOR]

In the framework of simplified quantum chemistry methods, we introduce the eXact integral simplified time-dependent density functional theory (XsTD-DFT). This method is based on the simplified time-dependent density functional theory (sTD-DFT), where all semi-empirical two-electron integrals are replaced by exact one- and two-center two-electron integrals, while other approximations from sTD-DFT are kept. The performance of this new parameter-free XsTD-DFT method was benchmarked on excited state and (non)linear response properties, including ultra-violet/visible absorption, first hyperpolarizability, and two-photon absorption (2PA). For a set of 77 molecules, the results from the XsTDA approach were compared to the TDA data. XsTDA/B3LYP excitation energies only deviate on average by 0.14 eV from TDA while drastically cutting computational costs by a factor of 20 or more depending on the energy threshold chosen. The absolute deviations of excitation energies with respect to the full scheme are decreasing with increasing system size, showing the suitability of XsTDA/XsTD-DFT to treat large systems. Comparing XsTDA and its predecessor sTDA, the new scheme generally improves excitation energies and oscillator strengths, in particular, for charge transfer states. TD-DFT first hyperpolarizability frequency dispersions for a set of push-pull π-conjugated molecules are faithfully reproduced by XsTD-DFT, while the previous sTD-DFT method provides redshifted resonance energy positions. Excellent performance with respect to the experiment is observed for the 2PA spectrum of the enhanced green fluorescent protein. The obtained robust accuracy similar to TD-DFT at a fraction of the computational cost opens the way for a plethora of applications for large systems and in high throughput screening studies. [ABSTRACT FROM AUTHOR]

Proflavine, a fluorescent cationic dye with strong absorption in the visible, has been proposed as a potential contributor to diffuse interstellar bands (DIBs). To investigate this hypothesis, it is essential to examine the spectra of cold and isolated ions for comparison. Here, we report absorption spectra of proflavine ions, trapped in a liquid-nitrogen-cooled ion trap filled with helium-buffer gas, as well as fluorescence spectra to provide further information on the intrinsic photophysics. We find absorption- and fluorescence-band maxima at 434.2 ± 0.1 and 434.7 ± 0.3 nm, corresponding to a Stokes shift of maximum 48 cm−1, which indicates minor differences between ground-state and excited-state geometries. Based on time-dependent density functional theory, we assign the emitting state to S2 as its geometry closely resembles that of S0, whereas the S1 geometry differs from that of S0. As a result, simulated spectra involving S1 exhibit long Franck-Condon progressions, absent in the experimental spectra. The latter displays well-resolved vibrational features, assigned to transitions involving in-plane vibrational modes where the vibrational quantum number changes by one. Dominant transitions are associated with vibrations localized on the NH2 moieties. Experiments repeated at room temperature yield broader spectra with maxima at 435.5 ± 1 nm (absorption) and 438.0 ± 1 nm (fluorescence). We again conclude that prevalent fluorescence arises from S2, i.e., anti-Kasha behavior, in agreement with previous work. Excited-state lifetimes are 5 ± 1 ns, independent of temperature. Importantly, we exclude the possibility that a narrow DIB at 436.4 nm originates from cold proflavine cations as the band is redshifted compared to our absorption spectra. [ABSTRACT FROM AUTHOR]

There is a longstanding difficulty that time-dependent density functional theory relying on adiabatic local density approximation is not applicable to the electron dynamics, for example, for an initially excited state, such as in photochemical reactions. To overcome this, we develop non-adiabatic excited-state time-dependent GW molecular dynamics (TDGW) on the basis of the extended quasiparticle theory. Replacing Kohn–Sham orbitals/energies with correlated, interacting quasiparticle orbitals/energies allows the full correspondence to the excited-state surfaces and corresponding total energies, with satisfying extended Koopmans' theorem. We demonstrate the power of TDGW using methane photolysis, CH 4 → CH 3 • + H , an important initiation reaction for combustion/pyrolysis and hydrogen production of methane. We successfully explore several possible pathways and show how this reaction dynamics is captured accurately through simultaneously time-tracing all quasiparticle levels. TDGW scales as O ( N B 3 - 4 ) , where NB is the number of basis functions, which is distinctly advantageous to performing dynamics using configuration interaction and coupled cluster methods. [ABSTRACT FROM AUTHOR]

The sinking of alkali cations in superfluid 4He nanodroplets is investigated theoretically using liquid 4He time-dependent density functional theory at zero temperature. The simulations illustrate the dynamics of the buildup of the first solvation shell around the ions. The number of helium atoms in this shell is found to linearly increase with time during the first stages of the dynamics. This points to a Poissonian capture process, as concluded in the work of Albrechtsen et al. on the primary steps of Na+ solvation in helium droplets [Albrechtsen et al., Nature 623, 319 (2023)]. The energy dissipation rate by helium atom ejection is found to be quite similar between all alkalis, the main difference being a larger energy dissipated per atom for the lighter alkalis at the beginning of the dynamics. In addition, the number of helium atoms in the first solvation shell is found to be lower at the end of the dynamics than at equilibrium for both Li+ and Na+, pointing to a kinetic rather than thermodynamical control of the snowball size for small and strongly attractive ions. [ABSTRACT FROM AUTHOR]

This research examines the nonadiabatic dynamics of cyclobutanone after excitation into the n → 3s Rydberg S2 state. It stems from our contribution to the Special Topic of the Journal of Chemical Physics to test the predictive capability of computational chemistry against unseen experimental data. Decoherence-corrected fewest-switches surface hopping was used to simulate nonadiabatic dynamics with full and approximated nonadiabatic couplings. Several simulation sets were computed with different electronic structure methods, including a multiconfigurational wavefunction [multiconfigurational self-consistent field (MCSCF)] specially built to describe dissociative channels, multireference semiempirical approach, time-dependent density functional theory, algebraic diagrammatic construction, and coupled cluster. MCSCF dynamics predicts a slow deactivation of the S2 state (10 ps), followed by an ultrafast population transfer from S1 to S0 (<100 fs). CO elimination (C3 channel) dominates over C2H4 formation (C2 channel). These findings radically differ from the other methods, which predicted S2 lifetimes 10–250 times shorter and C2 channel predominance. These results suggest that routine electronic structure methods may hold low predictive power for the outcome of nonadiabatic dynamics. [ABSTRACT FROM AUTHOR]

In this work, the ultrafast intramolecular rotation behavior of 1,1,2,3,4,5-hexaphenylsilole has been investigated in several solutions with different viscosities using femtosecond transient absorption spectroscopy combined with density functional theory and time-dependent density functional theory calculations. It is demonstrated that the nonradiative process, which competes with radiative decay, involves two main stages, namely the restricted intramolecular rotation and internal conversion processes. The intramolecular rotation depends on viscosity and presents a significant restriction. The restricted rotational rate is determined to be dozens of picoseconds. The following nonradiative process is strongly dominated by intramolecular rotation. The nonradiative decay rate will decrease with the increase in viscosity, leading to a rise in the radiative probability and photoluminous yield. These results have borne out the mechanism of ultrafast restricted intramolecular rotation of aggregation induced emission and provided a detailed photophysical picture of nonradiative processes. [ABSTRACT FROM AUTHOR]

The projector augmented wave (PAW) method of Blöchl linearly maps smooth pseudo wavefunctions to the highly oscillatory all-electron DFT orbitals. Compared to norm-conserving pseudopotentials (NCPP), PAW has the advantage of lower kinetic energy cutoffs and larger grid spacing at the cost of having to solve for non-orthogonal wavefunctions. We earlier developed orthogonal PAW (OPAW) to allow the use of PAW when orthogonal wavefunctions are required. In OPAW, the pseudo wavefunctions are transformed through the efficient application of powers of the PAW overlap operator with essentially no extra cost compared to NCPP methods. Previously, we applied OPAW to DFT. Here, we take the first step to make OPAW viable for post-DFT methods by implementing it in real-time time-dependent (TD) DFT. Using fourth-order Runge–Kutta for the time-propagation, we compare calculations of absorption spectra for various organic and biological molecules and show that very large grid spacings are sufficient, 0.6–0.7 bohr in OPAW-TDDFT rather than the 0.4–0.5 bohr used in traditional NCPP-TDDFT calculations. This reduces the memory and propagation costs by around a factor of 3. Our method would be directly applicable to any post-DFT methods that require time-dependent propagations such as the GW approximation and the Bethe–Salpeter equation. [ABSTRACT FROM AUTHOR]

The performance of SiC-based metal-oxide-semiconductor field-effect transistors (MOSFETs) degrades seriously after a period of continuous operation. To directly understand this issue, we conduct real-time time-dependent density functional theory (TDDFT) simulations on a series of nitrogen passivated SiC– SiO 2 interfaces to monitor the interaction between carriers and interface atoms. We find that the nitrogen passivation always leaves behind two local states near the VBM, which gives a chance to the strong interaction between channel carriers and C–N bonds, and finally results in the generation of C dangling bond defects. These processes are vividly presented and confirmed by the TDDFT simulation. Additionally, the results show that the new defects are more easily formed by the passivated C cluster than the passivated Si vacancy. These studies provide physical insights into the degradation mechanisms of working SiC MOSFETs, while simultaneously demonstrating the advantage of TDDFT as a crucial tool for investigating defect generation dynamics in semiconductor devices. [ABSTRACT FROM AUTHOR]

The light-harvesting excitonic properties of poly(phenylene ethynylene) (PPE) extended dendrimers (tree-like π-conjugated macromolecules) involve a directional cascade of local excitation energy transfer (EET) processes occurring from the "leaves" (shortest branches) to the "trunk" (longest branch), which can be viewed from a vibronic perspective as a sequence of internal conversions occurring among a connected graph of nonadiabatically coupled locally excited electronic states via conical intersections. The smallest PPE building block that is able to exhibit EET, the asymmetrically meta-substituted PPE oligomer with one acetylenic bond on one side and two parallel ones on the other side (hence, 2-ring and 3-ring para-substituted pseudo-fragments), is a prototype and the focus of the present work. From linear-response time-dependent density functional theory electronic-structure calculations of the molecule as regards its first two nonadiabatically coupled, optically active, singlet excited states, we built a (1 + 2)-state-8-dimensional vibronic-coupling Hamiltonian model for running subsequent multiconfiguration time-dependent Hartree wavepacket relaxations and propagations, yielding both steady-state absorption and emission spectra as well as real-time dynamics. The EET process from the shortest branch to the longest one occurs quite efficiently (about 80% quantum yield) within the first 25 fs after light excitation and is mediated vibrationally through acetylenic and quinoidal bond-stretching modes together with a particular role given to the central-ring anti-quinoidal rock-bending mode. Electronic and vibrational energy relaxations, together with redistributions of quantum populations and coherences, are interpreted herein through the lens of a nonadiabatic perspective, showing some interesting segregation among the foremost photoactive degrees of freedom as regards spectroscopy and reactivity. [ABSTRACT FROM AUTHOR]

A nitrogen K-edge x-ray absorption near-edge structure (XANES) survey is presented for tetrapyrido[3,2-a:2′,3′-c:3″,2″-h:2‴,3‴-j]phenazine (tpphz)-bridged bimetallic assemblies that couple chromophore and catalyst transition metal complexes for light driven catalysis, as well as their individual molecular constituents. We demonstrate the high N site sensitivity of the N pre-edge XANES features, which are energetically well-separated for the phenazine bridge N atoms and for the individual metal-bound N atoms of the inner coordination sphere ligands. By comparison with the time-dependent density functional theory calculated spectra, we determine the origins of these distinguishable spectral features. We find that metal coordination generates large shifts toward higher energy for the metal-bound N atoms, with increasing shift for 3d < 4d < 5d metal bonding. This is attributed to increasing ligand-to-metal σ donation that increases the effective charge of the bound N atoms and stabilizes the N 1s core electrons. In contrast, the phenazine bridge N pre-edge peak is found at a lower energy due to stabilization of the low energy electron accepting orbital localized on the phenazine motif. While no sensitivity to ground state electronic coupling between the individual molecular subunits was observed, the spectra are sensitive to structural distortions of the tpphz bridge. These results demonstrate N K-edge XANES as a local probe of electronic structure in large bridging ligand motifs, able to distinctly investigate the ligand-centered orbitals involved in metal-to-ligand and ligand-to-ligand electron transfer following light absorption. [ABSTRACT FROM AUTHOR]

In this work, charge photogeneration and recombination processes of PM6:IDIC-4F and PM6:IDIC blend films were investigated by the steady-state and time-resolved spectroscopies, as well as the time-dependent density functional theory calculations. The peaks in absorption and photoluminescence (PL) spectra of IDIC and IDIC-4F solutions were assigned by combining the experiment and the simulation of UV–vis absorption and PL spectra. For neat acceptor films, the exciton diffusion length of neat IDIC and IDIC-4F films was estimated as ∼28.9 and ∼19.9 nm, respectively. For PM6-based blend films, we find that the fluorine substitution engineering on the IDIC acceptor material can increase the phase separate size of acceptor material in blend films, resulting in the reduction of dissociation efficiencies of acceptor excitons. In addition, we find that the charge recombination in PM6:IDIC-4F is dominated by bimolecular recombination, in comparison to geminate type carrier recombination in PM6:IDIC blend films. In addition, we find that thermal annealing treatment has a weak influence on carrier recombination but slightly reduces the exciton dissociation efficiency of acceptor in PM6:IDIC blend films, leading to a slightly reduced power conversion efficiency of PM6:IDIC solar cells. These results may shed light on the design of high-performance semiconductor molecules for application in solar cells. [ABSTRACT FROM AUTHOR]

We present a novel theoretical formulation for performing quantum dynamics in terms of moments within the single-particle description. By expressing the quantum dynamics in terms of increasing orders of moments, instead of single-particle wave functions as generally done in time-dependent density functional theory, we describe an approach for reducing the high computational cost of simulating the quantum dynamics. The equation of motion is given for the moments by deriving analytical expressions for the first-order and second-order time derivatives of the moments, and a numerical scheme is developed for performing quantum dynamics by expanding the moments in the Taylor series as done in classical molecular dynamics simulations. We propose a few numerical approaches using this theoretical formalism on a simple one-dimensional model system, for which an analytically exact solution can be derived. The application of the approaches to an anharmonic system is also discussed to illustrate their generality. We also discuss the use of an artificial neural network model to circumvent the numerical evaluation of the second-order time derivatives of the moments, as analogously done in the context of classical molecular dynamics simulations. [ABSTRACT FROM AUTHOR]

The use of truncated configuration interaction in real-time time-dependent simulations of electron dynamics provides a balance of computational cost and accuracy, while avoiding some of the failures associated with real-time time-dependent density functional theory. However, low-order truncated configuration interaction also has limitations, such as overestimation of polarizability in configuration interaction singles, even when perturbative doubles are included. Increasing the size of the determinant expansion may not be computationally feasible, and so, in this work, we investigate the use of nonorthogonality in the determinant expansion to establish the extent to which higher-order substitutions can be recovered, providing an improved description of electron dynamics. Model systems are investigated to quantify the extent to which different methods accurately reproduce the (hyper)polarizability, including the high-harmonic generation spectrum of H2, water, and butadiene. [ABSTRACT FROM AUTHOR]

Strong light–matter interactions significantly modify the optical properties of molecules in the vicinity of plasmonic metal nanoparticles. Since the dimension of the plasmonic cavity approaches that of the molecules, it is critical to explicitly describe the nanoparticle junctions. In this work, we use the discrete interaction model/quantum mechanical (DIM/QM) method to model the coupling between the plasmonic near-field and molecular excited states. DIM/QM is a combined electrodynamics/quantum mechanical model that uses an atomistic description of the nanoparticle. We extend the DIM/QM method to include the local field effects in the sum-over-state formalism of time-dependent density functional theory. As a test of the method, we study the interactions between small organic chromophores and metal nanoparticles. In particular, we examine how the inclusion of multiple electronic transitions and intermolecular interactions modify the coupling between molecules and nanoparticles. Using the sum-over-state formalism of DIM/QM, we show that two-state models break down when the plasmon excitation is detuned from the molecular excitations. To gain further insight, we compare the simple coupled-dipole model (CDM) with the DIM/QM model. We find that CDM works well for simple systems but fails when going beyond the single molecule or single nanoparticle cases. We also find that the coupling depends strongly on the site of the nanoparticle in which the chromophore couples to. Our work suggests the importance of explicitly describing the cavity to capture the atomistic level local field environment in which the molecule strongly couples to. [ABSTRACT FROM AUTHOR]

Ultraviolet and vacuum ultraviolet photo-absorption spectra of azido (–N3)-based energetic plasticizer, bis(1,3-diazido-prop-2-yl)-malonate (abbreviated as BDAzPM), in the gas phase is recorded at room temperature and in the photon energy range of 5.5–9.9 eV using a synchrotron radiation source. Complementary computational results obtained using the time-dependent density functional theory document the vertical transition energies and oscillator strengths. Comparison of the simulated spectra with the experimental absorption spectrum of BDAzPM reveals that the early part of the absorption spectrum of BDAzPM is of pure valence excitation character, whereas the later intense part of the absorption spectrum is dominated by mixed Rydberg and valence electronic excitations. [ABSTRACT FROM AUTHOR]

Modeling excited state processes in molecular crystals is relevant for several applications. A popular approach for studying excited state molecular crystals is to use cluster models embedded in point charges. In this paper, we compare the performance of several embedding models in predicting excited states and S1–S0 optical gaps for a set of crystals from the X23 molecular crystal database. The performance of atomic charges based on ground or excited states was examined for cluster models, Ewald embedding, and self-consistent approaches. We investigated the impact of various factors, such as the level of theory, basis sets, embedding models, and the level of localization of the excitation. We consider different levels of theory, including time-dependent density functional theory and Tamm–Dancoff approximation (TDA) (DFT functionals: ωB97X-D and PBE0), CC2, complete active space self-consistent field, and CASPT2. We also explore the impact of selection of the QM region, charge leakage, and level of theory for the description of different kinds of excited states. We implemented three schemes based on distance thresholds to overcome overpolarization and charge leakage in molecular crystals. Our findings are compared against experimental data, G0W0-BSE, periodic TDA, and optimally tuned screened range-separated functionals. [ABSTRACT FROM AUTHOR]

Time-dependent density functional theory within the linear response regime provides a solid mathematical framework to capture excitations. The accuracy of the theory, however, largely depends on the approximations for the exchange–correlation (xc) kernels. Away from the long-wavelength (or q = 0 short wave-vector) and zero-frequency (ω = 0) limit, the correlation contribution to the kernel becomes more relevant and dominant over exchange. The dielectric function, in principle, can encompass xc effects relevant to describe low-density physics. Furthermore, besides collective plasmon excitations, the dielectric function can reveal collective electron–hole excitations, often dubbed "ghost excitons." Besides collective excitons, the physics of the low-density regime is rich, as exemplified by a static charge-density wave that was recently found for rs > 69, and was shown to be associated with softening of the plasmon mode. These excitations are seen to be present in much higher density 2D homogeneous electron gases of rs ≳ 4. In this work, we perform a thorough analysis with xc model kernels for excitations of various nature. The uniform electron gas, as a useful model of real metallic systems, is used as a platform for our analysis. We highlight the relevance of exact constraints as we display and explain screening and excitations in the low-density region. [ABSTRACT FROM AUTHOR]

Conical intersections constitute the conceptual bedrock of our working understanding of ultrafast, nonadiabatic processes within photochemistry (and photophysics). Accurate calculation of potential energy surfaces within the vicinity of conical intersections, however, still poses a serious challenge to many popular electronic structure methods. Multiple works have reported on the deficiency of methods like linear-response time-dependent density functional theory within the adiabatic approximation (AA LR-TDDFT) or algebraic diagrammatic construction to second-order [ADC(2)]—approaches often used in excited-state molecular dynamics simulations—to describe conical intersections between the ground and excited electronic states. In the present study, we focus our attention on conical intersections between excited electronic states and probe the ability of AA LR-TDDFT and ADC(2) to describe their topology and topography, using protonated formaldimine and pyrazine as two exemplar molecules. We also take the opportunity to revisit the performance of these methods in describing conical intersections involving the ground electronic state in protonated formaldimine—highlighting in particular how the intersection ring exhibited by AA LR-TDDFT can be perceived either as a (near-to-linear) seam of intersection or two interpenetrating cones, depending on the magnitude of molecular distortions within the branching space. [ABSTRACT FROM AUTHOR]

Although useful to extract excitation energies of states of double-excitation character in time-dependent density functional theory that are missing in the adiabatic approximation, the frequency-dependent kernel derived earlier [Maitra et al., J. Chem. Phys. 120, 5932 (2004)] was not designed to yield oscillator strengths. These are required to fully determine linear absorption spectra, and they also impact excited-to-excited-state couplings that appear in dynamics simulations and other quadratic response properties. Here, we derive a modified non-adiabatic kernel that yields both accurate excitation energies and oscillator strengths for these states. We demonstrate its performance on a model two-electron system, the Be atom, and on excited-state transition dipoles in the LiH molecule at stretched bond-lengths, in all cases producing significant improvements over the traditional approximations. [ABSTRACT FROM AUTHOR]

In this report, we successfully engineered a novel probe based on an acceptor–donor–acceptor (A–D–A) architecture featuring dicyanovinyl-substituted thieno[3,2-b]thiophene, termed DCVTT. The designed probe self-assembles into luminous nanoparticles (DCVTT NPs) upon introducing mixed aqueous solutions. These fluorescent nanostructures served as a ratiometric probe for detecting cyanide (CN−) ions in aqueous-based environments, owing to the robust Intramolecular Charge Transfer (ICT) characteristics of DCVTT. The A–D–A substituents in DCVTT significantly enhanced ICT behavior by promoting more efficient electron transfer between the donor and acceptor groups. This improved electron transfer process leads to heightened sensitivity in detection applications. In the case of cyanide (CN) sensing, this enhanced ICT behavior manifests as a strong colorimetric response, allowing for a visible color change before and after interaction with cyanide. Speculation regarding the interaction mechanism between DCVTT and CN− is proposed based on the findings of various experimental analyses. The detection limit (LOD) for DCVTT in identifying CN− is 0.83 nM, significantly lower than the CN− concentration thresholds deemed safe by the World Health Organization (WHO) and the United States Environmental Protection Agency (EPA). Time-Dependent Density Functional Theory (TD-DFT) has been utilized to theoretically analyze the optical properties of DCVTT both before and after the introduction of the CN− ions. A paper-based test strip was developed to demonstrate its practical application to enable efficient qualitative CN− detection by visual inspection. Furthermore, this sensing platform demonstrates highly accurate quantitative detection of CN− in apple seeds. No prior reports have utilized fluorescence techniques to estimate apple seeds' CN levels. [ABSTRACT FROM AUTHOR]