Excited State Dynamics Research Articles

Recombination zone shift in OLEDs of the pyrene- phenanthroimidazole conjugate giving cyan and green emission

Phenanthroimidazole derivative with Pyrene (PhenI-Py), which is known to be a good blue emitter, has been used to make OLED devices. We report the tuning of the emission from green (peak emission at 535 nm) to cyan (peak emission at 495 nm) in OLEDs by changing the device geometry using different hole transporting layers (HTL). Cyan OLEDs reported a high external quantum efficiency (EQE) of ∼10%. By making devices with different thicknesses of the active layer and hole transporting layers (HTL), this wavelength shift could be understood on the basis of the shift in the recombination zone (RZ). Time resolved area normalized emission spectroscopy (TRANES) carried out in thin films of PhenI-Py indicated the dynamics of excited states, which seem to be responsible for the observed RZ shift. Thus, our results present an understanding of the mechanism of the observed colour tunability in devices of PhenI-Py.

Establishing the origin of Marcus-inverted-region behaviour in the excited-state dynamics of cobalt(III) polypyridyl complexes.

Growing interest in the use of first-row transition metal complexes in a number of applied contexts-including but not limited to photoredox catalysis and solar energy conversion-underscores the need for a detailed understanding of their photophysical properties. A recent focus on ligand-field photocatalysis using cobalt(III) polypyridyls in particular has unlocked unprecedented excited-state reactivities. Photophysical studies on Co(III) chromophores in general are relatively uncommon, and so here we carry out a systematic study of a series of Co(III) polypyridyl complexes in order to delineate their excited-state dynamics. Compounds with varying ligand-field strengths were prepared and studied using variable-temperature ultrafast transient absorption spectroscopy. Analysis of the data establishes that the ground-state recovery dynamics are operating in the Marcus inverted region, in stark contrast to what is typically observed in other first-row metal complexes. The analysis has further revealed the underlying reasons driving this excited-state behaviour, thereby enabling potential advancements in the targeted use of the Marcus inverted region for a variety of photolytic applications.

TADF Blue Emitters with Balanced π-Conjugation─Design, Synthesis, Spectral Characterization, and a Model OLED with 8-(5-(tert-Butyl)-1,3,4-oxadiazol-2-yl)-N,N-bis(4-(tert-butyl)phenyl)dibenzo[b,d]furan-2-amine.

Blue organic light-emitting diodes (OLED) suffer from relatively short lifetimes and a comparatively low lighting efficiency. One of the approaches to improving their characteristics is the development of luminophores with the potential for thermally activated delayed fluorescence (TADF). Herein, a set of donor-spacer-acceptor compounds with potential for TADF are designed, synthesized, and computationally and spectroscopically characterized. The excited state dynamics of the most prospective dye is monitored by time-resolved fluorescence and transient absorption spectroscopy. The experimental data are obtained and processed by a newly developed method and supplemented by quantum chemical calculations. The comprehensive approach allowed rationalization of the complex cascade-type photophysical behavior. The most promising emitter is included in an OLED displaying a blue color with a maximum EQE of 4.9% and negligible efficiency roll-off at higher luminance.

Ultrafast Hot Exciton Nonadiabatic Excited-State Dynamics in Green Fluorescent Protein Chromophore Analogue.

The ultrafast high-energy nonadiabatic excited-state dynamics of the benzylidenedimethylimidazolinone chromophore dimer has been investigated using an electronic structure method coupled with on-the-fly quantitative wave function analysis to gain insight into the photophysics of hot excitons in biological systems. The dynamical simulation provides a rationalization of the behavior of the exciton in a dimer after the photoabsorption of light to higher-energy states. The results suggest that hot exciton localization within the manifold of excited states is caused by the hindrance of torsional rotation due to imidazolinone (I) or phenolate (P) bonds i.e., ΦI- or ΦP-dihedral rotation, in the monomeric units of a dimer. This hindrance arises due to weak π-π stacking interaction in the dimer, resulting in an energetically uphill excited-state barrier for ΦI- and ΦP-twisted rotation, impeding the isomerization process in the chromophore. Thus, this study highlights the potential impact of the weak π-π interaction in regulating the photodynamics of the green fluorescent protein chromophore derivatives.

Exploring the World of Curcumin: Photophysics, Photochemistry, and Applications in Nanoscience and Biology.

Curcumin is a bright yellow naturally occurring polyphenol which is the principal component of turmeric. It is used as herbal supplement, cosmetics ingredient, and food coloring agent. Over the years, the therapeutic properties of the natural product curcumin have gone unexploited but not unnoticed. Curcumin cannot be employed as a drug due to limitations such as low aqueous solubility and limited bioavailability. Many attempts have been made to overcome these limitations by confining the drug in various confined media to enhance its bioavailability. The biomolecule is emissive and undergoes fundamental excited state processes such as solvation dynamics and excited state intramolecular proton transfer (ESIPT). Curcumin based biomaterials and nanomaterials are also a fast advancing field where curcumin is an intrinsic component necessary for formation of these materials and no longer added as an external free drug. In this review, we will summarize the recent research on the photophysical and photochemical properties of curcumin and its excited state dynamics in various bio-mimicking systems. At the same time we wish to also incorporate the various applications of curcumin, especially in biology. Lastly due to the growing importance of materials science, we will briefly discuss some recent advances on curcumin based biomaterials and nanomaterials. We believe such a compilation of recent research surrounding curcumin will provide an overall understanding of its potentialities in different areas.

Inter-Oligomer Interaction Influence on Photoluminescence in Cis-Polyacetylene Semiconductor Materials.

Semiconducting conjugated polymers (CPs) are pivotal in advancing organic electronics, offering tunable properties for solar cells and field-effect transistors. Here, we carry out first-principle calculations to study individual cis-polyacetylene (cis-PA) oligomers and their ensembles. The ground electronic structures are obtained using density functional theory (DFT), and excited state dynamics are explored by computing nonadiabatic couplings (NACs) between electronic and nuclear degrees of freedom. We compute the nonradiative relaxation of charge carriers and photoluminescence (PL) using the Redfield theory. Our findings show that electrons relax faster than holes. The ensemble of oligomers shows faster relaxation compared to the single oligomer. The calculated PL spectra show features from both interband and intraband transitions. The ensemble shows broader line widths, redshift of transition energies, and lower intensities compared to the single oligomer. This comparative study suggests that the dispersion forces and orbital hybridizations between chains are the leading contributors to the variation in PL. It provides insights into the fundamental behaviors of CPs and the molecular-level understanding for the design of more efficient optoelectronic devices.

Long Excited-State Lifetimes in Three-Coordinate Copper(I) Complexes via Triplet-Triplet Energy Transfer to Pyrene-Decorated Isocyanides.

There has been much effort to improve excited-state lifetimes in photosensitizers based on earth-abundant first-row transition metals. Copper(I) complexes have gained significant attention in this field, and in most cases, sterically driven approaches are used to optimize their lifetimes. This study presents a series of three-coordinate copper(I) complexes (Cu1-Cu3) where the excited-state lifetime is extended by triplet-triplet energy transfer. The heteroleptic compounds feature a cyclohexyl-substituted β-diketiminate (CyNacNacMe) paired with aryl isocyanide ligands, giving the general formula Cu(CyNacNacMe)(CN-Ar) (CN-dmp = 2,6-dimethylphenyl isocyanide for Cu1; CN-pyr = 1-pyrenyl isocyanide for Cu2; CN-dmp-pyr = 2,6-dimethyl-4-(1-pyrenyl)phenyl isocyanide for Cu3). The nature, energies, and dynamics of the low-energy triplet excited states are assessed with a combination of photoluminescence measurements at room temperature and 77 K, ultrafast transient absorption (UFTA) spectroscopy, and DFT calculations. The complexes with the pyrene-decorated isocyanides (Cu2 and Cu3) exhibit extended excited-state lifetimes resulting from triplet-triplet energy transfer (TTET) between the short-lived charge-transfer excited state (3CT) and the long-lived pyrene-centered triplet state (3pyr). This TTET process is irreversible in Cu3, producing exclusively the 3pyr state, and in Cu2, the 3CT and 3pyr states are nearly isoenergetic, enabling reversible TTET and long-lived 3CT luminescence. The improved photophysical properties in Cu2 and Cu3 result in improvements in activity for both photocatalytic stilbene E/Z isomerization via triplet energy transfer and photoredox transformations involving hydrodebromination and C-O bond activation. These results illustrate that the extended excited-state lifetimes achieved through TTET result in newly conceived photosynthetically relevant earth-abundant transition metal complexes.

Construction of Highly Accurate Machine Learning Potential Energy Surfaces for Excited-State Dynamics Simulations Based on Low-Level Data Sets.

Machine learning is capable of effectively predicting the potential energies of molecules in the presence of high-quality data sets. Its application in the construction of ground- and excited-state potential energy surfaces is attractive to accelerate nonadiabatic molecular dynamics simulations of photochemical reactions. Because of the huge computational cost of excited-state electronic structure calculations, the construction of a high-quality data set becomes a bottleneck. In the present work, we first built two data sets. One was obtained from surface hopping dynamics simulations at the semiempirical OM2/MRCI level. Another was extracted from the dynamics trajectories at the CASSCF level, which was reported previously. The ground- and excited-state potential energy surfaces of ethylene-bridged azobenzene at the CASSCF computational level were constructed based on the former low-level data set. Although non-neural network machine learning methods can achieve good or modest performance during the training process, only neural network models provide reliable predictions on the latter external test data set. The BPNN and SchNet combined with the Δ-ML scheme and the force term in the loss functions are recommended for dynamics simulations. Then, we performed excited-state dynamics simulations of the photoisomerization of ethylene-bridged azobenzene on machine learning potential energy surfaces. Compared with the lifetimes of the first excited state (S1) estimated at different computational levels, our results on the E isomer are in good agreement with the high-level estimation. However, the overestimation of the Z isomer is unimproved. It suggests that smaller errors during the training process do not necessarily translate to more accurate predictions on high-level potential energies or better performance on nonadiabatic dynamics simulations, at least in the present case.

Spin-Correlated Luminescence of a Carbazole-Containing Diradical Emitter: Single-Molecule Magnetoluminescence and Thermally Activated Emission.

Luminescent radicals have been intensively studied as a new class of materials exhibiting novel photofunctions unique to open-shell systems. When luminescent radicals are assembled, intriguing spin-correlated luminescence phenomena emerge, including excimer-like emission and magnetic-field effects on luminescence (i.e., magnetoluminescence, MagLum). However, the underlying mechanisms of these phenomena arising from spin multiplicity and spin-dependent excited-state dynamics are poorly understood due to the limited number of luminescent polyradical systems available for study. In particular, the correlation between stronger intramolecular exchange interactions (|2J/kB| > ∼10 K, where J and kB are the intramolecular exchange coupling constant and the Boltzmann constant, respectively) and luminescence properties has not been fully explained. In this study, a novel carbazole-containing diradical emitter (1) and the corresponding monoradical (2) were prepared for the in-depth study of spin-correlated luminescence properties, with luminescence measurements under magnetic fields of up to 18 T. Diradical 1 has a negative 2J/kB value of several tens of kelvin and exhibits a single-molecule MagLum and thermally activated luminescence, whereas 2 does not. Detailed quantitative analyses revealed that both the spin-correlated luminescence properties of 1 are strongly dominated by ground-state spin statistics based on the Boltzmann distribution (i.e., 2J/kB values). Furthermore, diradical 1 exhibits external heavy-atom effects in heavy-atom-containing solvents such as iodobenzene, whereas monoradical 2 does not. This is the first experimental verification of external heavy-atom effects in polyradical emitters. This work demonstrates that polyradical emitters can be designed based on spin degrees of freedom in both ground and excited states.

The Excited-State N-H Tautomerization Rate in Free-Base Corroles.

Corrole is a tetrapyrrolic dye with a structure that resembles porphyrin, apart from a single missing carbon. The absence of this carbon results in the re-arrangement of the double bonds within the macrocycle, and the presence of three pyrrolic protons in the central cavity in its free-base form. These protons lead to the existence of two distinct tautomeric structures that exist in a dynamic equilibrium. Although the ground-state energies of the tautomers are similar, the excited states show a significant difference in energy which unbalances the equilibrium between the tautomers and results in rapid excited-state tautomerization, favouring one tautomeric species over the other. Although the excited-state tautomerization process has been known for a long time, very few studies have been performed on it, leaving many key aspects of the process poorly understood. Herein we show how ultrafast photoluminescence can be used to experimentally determine the rates of excited-state tautomerization and activation energies of three free-base corrole derivatives thus allowing us to completely describe the excited-state dynamics of the unusual excited state of free-base corrole and opening the door to the development of new materials that can exploit its unique characteristics.

Managing temperature in open quantum systems strongly coupled with structured environments.

In non-perturbative non-Markovian open quantum systems, reaching either low temperatures with the hierarchical equations of motion (HEOM) or high temperatures with the Thermalized Time Evolving Density Operator with Orthogonal Polynomials Algorithm (T-TEDOPA) formalism in Hilbert space remains challenging. We compare different ways of modeling the environment. Sampling the Fourier transform of the bath correlation function, also called temperature dependent spectral density, proves to be very effective. T-TEDOPA [Tamascelli et al., Phys. Rev. Lett. 123, 090402 (2019)] uses a linear chain of oscillators with positive and negative frequencies, while HEOM is based on the complex poles of an optimized rational decomposition of the temperature dependent spectral density [Xu et al., Phys. Rev. Lett. 129, 230601 (2022)]. Resorting to the poles of the temperature independent spectral density and of the Bose function separately is an alternative when the problem due to the huge number of Bose poles at low temperatures is circumvented. Two examples illustrate the effectiveness of the HEOM and T-TEDOPA approaches: a benchmark pure dephasing case and a two-bath model simulating the dynamics of excited electronic states coupled through a conical intersection. We show the efficiency of T-TEDOPA to simulate dynamics at a finite temperature by using either continuous spectral densities or only all the intramolecular oscillators of a linear vibronic model calibrated from abinitio data of a phenylene ethynylene dimer.

Nonadiabatic molecular dynamics with subsystem density functional theory: application to crystalline pentacene

In this work, we report the development and assessment of the nonadiabatic molecular dynamics approach with the electronic structure calculations based on the linearly scaling subsystem density functional method. The approach is implemented in an open-source embedded Quantum Espresso/Libra software specially designed for nonadiabatic dynamics simulations in extended systems. As proof of the applicability of this method to large condensed-matter systems, we examine the dynamics of nonradiative relaxation of excess excitation energy in pentacene crystals with the simulation supercells containing more than 600 atoms. We find that increased structural disorder observed in larger supercell models induces larger nonadiabatic couplings of electronic states and accelerates the relaxation dynamics of excited states. We conduct a comparative analysis of several quantum-classical trajectory surface hopping schemes, including two new methods proposed in this work (revised decoherence-induced surface hopping and instantaneous decoherence at frustrated hops). Most of the tested schemes suggest fast energy relaxation occurring with the timescales in the 0.7–2.0 ps range, but they significantly overestimate the ground state recovery rates. Only the modified simplified decay of mixing approach yields a notably slower relaxation timescales of 8–14 ps, with a significantly inhibited ground state recovery.

Ultrafast terahertz Stark spectroscopy reveals the excited-state dipole moments of retinal in bacteriorhodopsin

The photoinduced all-trans to 13-cis isomerization of the retinal Schiff base represents the ultrafast first step in the reaction cycle of bacteriorhodopsin (BR). Extensive experimental and theoretical work has addressed excited-state dynamics and isomerization via a conical intersection with the ground state. In conflicting molecular pictures, the excited state potential energy surface has been modeled as a pure S[Formula: see text] state that intersects with the ground state, or in a 3-state picture involving the S[Formula: see text] and S[Formula: see text] states. Here, the photoexcited system passes two crossing regions to return to the ground state. The electric dipole moment of the Schiff base in the S[Formula: see text] and S[Formula: see text] state differs strongly and, thus, its measurement allows for assessing the character of the excited-state potential. We apply the method of ultrafast terahertz (THz) Stark spectroscopy to measure electric dipole changes of wild-type BR and a BR D85T mutant upon electronic excitation. A fully reversible transient broadening and spectral shift of electronic absorption is induced by a picosecond THz field of several megavolts/cm and mapped by a 120-fs optical probe pulse. For both BR variants, we derive a moderate electric dipole change of 5 [Formula: see text] 1 Debye, which is markedly smaller than predicted for a neat S[Formula: see text]-character of the excited state. In contrast, S[Formula: see text]-admixture and temporal averaging of excited-state dynamics over the probe pulse duration gives a dipole change in line with experiment. Our results support a picture of electronic and nuclear dynamics governed by the interaction of S[Formula: see text] and S[Formula: see text] states in a 3-state model.

Ultrafast dual-fluorescence dynamics of 2-(2'-hydroxyphenyl) benzimidazole by femtosecond transient absorption spectroscopy

2-(2'-Hydroxyphenyl) benzimidazole (HBI) and its derivatives are widely used in fluorescent probes, luminescent materials, and other sensing materials. In this study, the time-resolved fluorescence behaviour, and excited-state dynamics of HBI and 2-phenyl-1H-benzo[d]imidazole (BI) were studied using femtosecond transient absorption (fs-TA) spectroscopy. The stimulated emission (SE) and excited-state absorption signals of the BI molecule were located at 355 and 437 nm, respectively. For HBI, these signals were located at 475 and 384 nm, respectively. The SE signals of the BI and HBI molecules in their fs-TA spectra were consistent with the experimental short-wave fluorescence at 340 and 460 nm, respectively, in the steady-state spectra. The long-wave signal of HBI at 475 nm indicates its dual fluorescence, which may be caused by proton transfer or conformational torsion after photoexcitation. The large theoretical energy barrier of 40.97 kcal/mol in first excited (S1) state of HBI excludes the latter hypothesis. Additionally, the small energy barrier (1.88 kcal/mol) in the S1 state confirmed the excited-state intramolecular proton transfer (ESIPT). This indicates that ESIPT induces dual fluorescence behaviour of the HBI molecule, which was also demonstrated by the infrared spectra, theoretical fluorescence peaks, and molecular orbitals.

Time-Resolved X-ray Emission Spectroscopy and Synthetic High-Spin Model Complexes Resolve Ambiguities in Excited-State Assignments of Transition-Metal Chromophores: A Case Study of Fe-Amido Complexes.

To fully harness the potential of abundant metal coordination complex photosensitizers, a detailed understanding of the molecular properties that dictate and control the electronic excited-state population dynamics initiated by light absorption is critical. In the absence of detectable luminescence, optical transient absorption (TA) spectroscopy is the most widely employed method for interpreting electron redistribution in such excited states, particularly for those with a charge-transfer character. The assignment of excited-state TA spectral features often relies on spectroelectrochemical measurements, where the transient absorption spectrum generated by a metal-to-ligand charge-transfer (MLCT) electronic excited state, for instance, can be approximated using steady-state spectra generated by electrochemical ligand reduction and metal oxidation and accounting for the loss of absorptions by the electronic ground state. However, the reliability of this approach can be clouded when multiple electronic configurations have similar optical signatures. Using a case study of Fe(II) complexes supported by benzannulated diarylamido ligands, we highlight an example of such an ambiguity and show how time-resolved X-ray emission spectroscopy (XES) measurements can reliably assign excited states from the perspective of the metal, particularly in conjunction with accurate synthetic models of ligand-field electronic excited states, leading to a reinterpretation of the long-lived excited state as a ligand-field metal-centered quintet state. A detailed analysis of the XES data on the long-lived excited state is presented, along with a discussion of the ultrafast dynamics following the photoexcitation of low-spin Fe(II)-Namido complexes using a high-spin ground-state analogue as a spectral model for the 5T2 excited state.

Pd(II)‐TADF Emitters Featuring Multiple Intramolecular Noncovalent Interactions: Toward Organic Light‐Emitting Diodes with EQEs up to 31.5% and Operational Half‐Lifetimes Exceeding 1600 h at 3000 cd m−2

AbstractThe second‐row transition metal complexes have been much less exploited as emitters for organic light‐emitting diodes (OLEDs). Despite the considerable efforts to develop phosphorescent Pd(II) complexes by ligand design, the triplet excited states of Pd(II) complexes usually have very long lifetimes because of their ligand‐centered nature. Hereina panel of sandwich‐type mononuclear Pd(II) complexes is reported, namely PdDDBPZ, PdDTRZ, and PdDPYR, which exhibit strong yellow to red thermally activated delayed fluorescence (TADF) with photoluminescence quantum yields (PLQYs) of 87–94% in doped films. The metal ion plays a perturbing role in the intraligand charge transfer excited state dynamics, giving rise to accelerated reverse intersystem crossing (RISC). Owing to the space‐confined sandwich configuration, there are multiple noncovalent interactions within the molecules, which are qualitatively and quantitatively analyzed by theoretical calculations. The Pd(II) complexes show high device efficiencies with external quantum efficiencies (EQEs) up to 31.5%. The ultralow efficiency roll‐off is as low as 1% at 1000 cd m−2. The device operational stability test for PdDTRZ reveals a half‐lifetime (LT50) of 1615 h at an initial luminance of 3000 cd m−2. The leverage of metal‐promoted TADF mechanism together with intramolecular noncovalent interactions proves feasible for developing practical Pd(II)‐TADF emitters toward OLEDs.

Vibrational coherences in half-broadband 2D electronic spectroscopy: Spectral filtering to identify excited state displacements.

Vibrational coherences in ultrafast pump-probe (PP) and 2D electronic spectroscopy (2DES) provide insights into the excited state dynamics of molecules. Femtosecond coherence spectra and 2D beat maps yield information about displacements of excited state surfaces for key vibrational modes. Half-broadband 2DES uses a PP configuration with a white light continuum probe to extend the detection range and resolve vibrational coherences in the excited state absorption (ESA). However, the interpretation of these spectra is difficult as they are strongly dependent on the spectrum of the pump laser and the relative displacement of the excited states along the vibrational coordinates. We demonstrate the impact of these convoluting factors for a model based upon cresyl violet. A careful consideration of the position of the pump spectrum can be a powerful tool in resolving the ESA coherences to gain insights into excited state displacements. This paper also highlights the need for caution in considering the spectral window of the pulse when interpreting these spectra.

Charge Trapping and Defect Dynamics as Origin of Memory Effects in Metal Halide Perovskite Memlumors.

Large language models for artificial intelligence applications require energy-efficient computing. Neuromorphic photonics has the potential to reach significantly lower energy consumption in comparison with classical electronics. A recently proposed memlumor device uses photoluminescence output that carries information about its excitation history via the excited state dynamics of the material. Solution-processed metal halide perovskites can be used as efficient memlumors. We show that trapping of photogenerated charge carriers modulated by photoinduced dynamics of the trapping states themselves explains the memory response of perovskite memlumors on time scales from nanoseconds to minutes. The memlumor concept shifts the paradigm of the detrimental role of charge traps and their dynamics in metal halide perovskite semiconductors by enabling new applications based on these trap states. The appropriate control of defect dynamics in perovskites allows these materials to enter the field of energy-efficient photonic neuromorphic computing, which we illustrate by proposing several possible realizations of such systems.

Excited State Dynamics and Transport of Self-Trapped Excitons in Bi-Doped Cs2Na0.4Ag0.6In(1-y)BiyCl6 Double Perovskites.

Lead-free double perovskites (DPs) have become notable in white light emission applications due to the self-trapped exciton (STE) formation in the excited state. However, the mechanism understanding of the excited state dynamics and transport of STE remains ambiguous. Here, we demonstrate a new STE (Bi-STE) forming in tiny Bi-doped Cs2Na0.4Ag0.6InCl6, alongside its intrinsic STE (i-STE), resulting in the DPs photoluminescence quantum yield (PLQY) increasing to as high as >90%. The i-STE exhibits faster formation (60 fs) and slower relaxation dynamics (2.8 μs) compared to the Bi-STE. Moreover, we unveil that the Bi doping can augment the i-STE diffusion properties to attain a diffusion coefficient (diffusion length) of 0.012 cm2 s-1 (1.7 μm) at room temperature, indicating their promise in photovoltaic applications. Our results shed light on significant STE dynamics and transport mechanisms in DPs, providing a new roadmap for advancing existing and crafting new DPs in light emission applications.

Nonadiabatic Dynamics with Exact Factorization: Implementation and Assessment.

In this work, we report our implementation of several independent-trajectory mixed-quantum-classical (ITMQC) nonadiabatic dynamics methods based on exact factorization (XF) in the Libra package for nonadiabatic and excited-state dynamics. Namely, the exact factorization surface hopping (SHXF), mixed quantum-classical dynamics (MQCXF), and mean-field (MFXF) are introduced. Performance of these methods is compared to that of several traditional surface hopping schemes, such as the fewest-switches surface hopping (FSSH), branching-corrected surface hopping (BCSH), and the simplified decay of mixing (SDM), as well as conventional Ehrenfest (mean-field, MF) method. Based on a comprehensive set of 1D model Hamiltonians, we find the ranking SHXF ≈ MQCXF > BCSH > SDM > FSSH ≫ MF, with the BCSH sometimes outperforming the XF methods in terms of describing coherences. Although the MFXF method can yield reasonable populations and coherences for some cases, it does not conserve the total energy and is therefore not recommended. We also find that the branching correction for auxiliary trajectories is important for the XF methods to yield accurate populations and coherences. However, the branching correction can worsen the quality of the energy conservation in the MQCXF. Finally, we find that using the time-dependent Gaussian width approximation used in the XF methods for computing decoherence correction can improve the quality of energy conservation in the MQCXF dynamics. The parameter-free scheme of Subotnik for computing the Gaussian widths is found to deliver the best performance in situations where such widths are not known a priori.