arXiv subjects

Seogjoo J. Jang

Publications and source records attributed to Seogjoo J. Jang.

At least 19 recordsLinked to original sources

arXiv2026

Dimensional Control of Excitonic Interactions in Exfoliated 2D Molecular Crystals

Two-dimensional (2D) materials provide unique opportunities to tailor excited-state properties through reduced dimensionality, altered dielectric screening and layer-dependent structural reconstruction. While such effects have been widely explored in norganic systems, their realization in molecular crystals has been limited by the difficulty of controlling thickness at the atomic scale while preserving crystalline order. Here we show that tetracene and three other molecular crystals can be mechanically exfoliated into mono-, few- or multilayer flakes, while retaining crystalline order. This capability enables new studies of molecular crystals across a well defined thickness range within the same structural organization. Thickness-dependent spectra of these samples reveal how out-of-plane confinement modifies the excited-state energy landscape of tetracene: With decreasing thickness, the Davydov splitting diminishes, the Stokes shift increases, and signatures of more delocalized excitons emerge. Electron diffraction and exciton model-based analyses correlate these trends to changes in molecular packing, intermolecular coupling and dielectric screening. Our results also demonstrate that key features of molecular excitons can be systematically tuned by layer number, extending dimensional control from inorganic 2D materials to molecular crystals.

cond-mat.mtrl-sci↗

arXiv2026

Minimization of disorder as a key design principle for natural sizes of light harvesting 2 complexes

The light harvesting 2 (LH2) complex of purple bacteria has excellent energy conversion efficiency. Clarifying the design principle behind such efficiency at the atomistic level is crucial for understanding its structure-function relationship, and can be utilized for the design of artificial light harvesting systems. To this end, we conducted comprehensive computational investigation of the dynamical and statistical nature of electronic excited states of pigment molecules in a natural LH2 complex with 9-fold symmetry and its two non-natural {\it in silico} analogues with 6- and 12-fold symmetries. To ensure reliable and efficient all-atomistic molecular dynamics simulations, we combined a well established interpolation approach for the construction of the potential energy surface with a neural network machine learning approach. Outcomes of these calculations clarify that non-natural forms of LH2-type complexes have significantly larger quasistatic disorder than those for the natural one. In addition, non-natural systems have more disruptions of the hydrogen bonding, underscoring its crucial role for reducing the disorder. On the other hand, local environmental dynamics are relatively insensitive to the structural changes although there is moderate enhancement in the anharmonic or interatomic components for the synthetic ones. These findings based on all-atomistic simulations provide direct computational evidence that the structure and sizes of natural LH2 complexes are designed to minimize the energetic disorder. We analyze quantitative implications of these for the energy transferring capability of the LH2 complex.

physics.chem-ph↗

arXiv2026

Perspective of Fermi's golden rule and its generalizations in chemical physics

This perspective provides a succinct history of Fermi's golden rule (FGR), overview of its derivation, assumptions, and representative forms. Major applications of FGR, mostly in the field of chemical physics, are reviewed. These illustrate the broad applicability and success of FGR. Ambiguities and open issues encountered in practical applications of FGR are clarified. Recent advances in generalizations of FGR and computational methods for practical applications are addressed.

physics.chem-ph↗

arXiv2026

A simple fourth order propagator based on the Magnus expansion in the Liouville space: Application to a $Λ$-system and assessment of the rotating wave approximation

A simple 4th order propagator [Ture and Jang, {\it J. Phys. Chem. A.} {\bf 128}, 2871 (2024)] based on the Magnus expansion (ME) is extended to the Liouville space for both closed-system and Lindbladian open-system quantum dynamics. For both dynamics, commutator free versions of 4th order propagators are provided as well. These propagators are then applied to the dynamics of a driven $Λ$-system, where Lindblad terms represent the effect of a photonic bath. For both dynamics, the accuracy of the rotating wave approximation (RWA) for the matter-radiation interaction is assessed. We confirmed reasonable performance of RWA for weak and resonant fields. However, small errors appear for moderate fields and substantial errors can be found for strong fields where coherent population trapping can still be expected. We also found that the presence of bath for open system quantum dynamics consistently reduces the errors of the RWA. These results provide a quantitative information on how the RWA breaks down beyond weak field or for non-resonant cases. Major results are benchmarked against results of our 6th order ME-based propagator. We also provide numerical comparison of our algorithms with other 4th order algorithms for the $Λ$-system. These confirm reasonable performance of our simple propagators and the improvement gained through commutator-free expressions.

quant-ph↗

arXiv2026

Theoretical investigation of non-Förster exciton transfer mechanisms in perylene diimide donor, phenylene bridge, and terrylene diimide acceptor systems

The rates of exciton transfer within dyads of perylene diimide and terrylene diimide connected by oligophenylene bridge units have been shown to deviate significantly from those of Förster's resonance energy transfer theory, according to single molecule spectroscopy experiments. The present work provides a detailed computational and theoretical study investigating the source of such discrepancy. Electronic spectroscopy data are calculated by time-dependent density function theory and then compared with experimental results. Electronic couplings between exciton donor and acceptor are estimated based on both transition density cube method and transition dipole approximation. These results confirm that the delocalization of exciton to the bridge parts contribute to significant enhancement of donor-acceptor electronic coupling. Mechanistic details of exciton transfer are examined by estimating the contributions of the bridge electronic states, vibrational modes of the dyads commonly coupled to both donor and acceptor, inelastic resonance energy transfer mechanism, and dark exciton states. These analyses suggest that the contribution of common vibrational modes serves as the main source of deviation from Förster's spectral overlap expression.

physics.chem-ph↗

arXiv2026

Robust and fragile quantum effects in the transfer kinetics of delocalized excitons between B850 units of LH2 complexes

Aggregates of light harvesting 2 (LH2) complexes form the major exciton-relaying domain in the photosynthetic unit of purple bacteria. Application of a generalized master equation to pairs of the B850 units of LH2 complexes, where excitons predominantly reside, provide quantitative information on how the inter-LH2 exciton transfer depends on the distance, relative rotational angle, and the relative energies of the two LH2s. The distance dependence demonstrates significant enhancement of the rate due to quantum delocalization of excitons, the qualitative nature of which remains robust against the disorder. The angle dependence reflects isotropic nature of exciton transfer, which remains similar for the ensemble of disorder. The variation of the rate on relative excitation energies of LH2 exhibits resonance peaks, which however is fragile as the disorder becomes significant. Overall, the average transfer times between two LH2s are estimated to be in the range of 4 - 25 ps for physically plausible inter-LH2 distances.

physics.chem-ph↗

arXiv2026

Is There Elliptic Distortion in the Light Harvesting Complex 2 of Purple Bacteria?

Single molecule spectroscopy (SMS) revealed unusually large gap between two major exciton peaks of the B850 unit of light harvesting complex 2 (LH2), which could be explained assuming elliptic distortion or k=2 symmetry modulation in the site excitation energy. On the basis of extensive simulation of the SMS data and ensemble lineshape, we found that uniform modulation of k=2 symmetry cannot explain the dependence of intensity ratios on the gap of the two major peaks, which are available from SMS, nor the ensemble lineshape. Alternative models of disorder with k=1 and k=2 symmetry correlation are shown to reproduce these data reasonably well and can even explain the gap distribution when it is assumed that the lower major peak in the SMS lineshape is an intensity weighted average of k=1- and k=0 states.

physics.bio-ph↗

arXiv2026

Charge Hopping Dynamics along a Disordered Chain in Quantum Environments: Comparative Study of Different Rate Kernels

This work presents a computational study of charge hopping dynamics along a one dimensional chain with Gaussian site energy disorder and linearly coupled quantum bath. Time dependent square displacements are calculated directly from numerical solutions of Pauli master equations, for five different rate kernels: exact Fermi golden rule (FGR) rate expression, stationary phase interpolation (SPI) approximation, semiclassical (SC) approximation, classical Marcus rate expression, and Miller-Abrahams expression. All results demonstrate diffusive behavior in the steady state limit. The results based on the FGR rate expression show that the charge transport in quantum bath can be much more sensitive to the disorder than the prediction from the classical Marcus expression. While the SPI approximation captures this general trend reasonably well, the SC approximation tends to be unreliable at both quantitative and qualitative levels, and becomes even worse than the classical Marcus expression under certain conditions. These results offer useful guidance in the choice of approximate rate kernels for larger scale simulations, and also demonstrate significant but fragile positive effects of quantum environments on the charge hopping dynamics.

cond-mat.mtrl-sci↗

arXiv2026

Computational Modeling of Exciton-bath Hamiltonians for LH2 and LH3 Complexes of Purple Photosynthetic Bacteria at Room Temperature

Light harvesting 2 (LH2) complex is a primary component of the photosynthetic unit of purple bacteria that is responsible for harvesting and relaying excitons. The electronic absorption line shape of LH2 contains two major bands at 800 nm and 850 nm wavelength regions. Under low light condition, some species of purple bacteria replace LH2 with LH3, a variant form with almost the same structure as the former but with distinctively different spectral features. The major difference between the absorption line shapes of LH2 and LH3 is the shift of the 850 nm band of the former to a new 820 nm region. The microscopic origin of this difference has been subject to some theoretical/computational investigations. However, the genuine molecular level source of such difference is not clearly understood yet. This work reports a comprehensive computational study of LH2 and LH3 complexes so as to clarify different molecular level features of LH2 and LH3 complexes and to construct simple exciton-bath models with a common form. All-atomistic molecular dynamics (MD) simulations of both LH2 and LH3 complexes provide detailed molecular level structural differences of BChls in the two complexes, in particular, in their patterns of hydrogen bonding (HB) and torsional angles of the acetyl group. Time-dependent density functional theory calculation of the excitation energies of BChls for structures sampled from the MD simulations, suggests that the observed differences in HB and torsional angles cannot fully account for the experimentally observed spectral shift of LH3. Potential sources that can explain the actual spectral shift of LH3 are discussed, and their magnitudes are assessed through fitting of experimental line shapes.

physics.bio-ph↗

arXiv2026

Effects of Donor-Acceptor Quantum Coherence and Non-Markovian Bath on the Distance Dependence of Resonance Energy Transfer

Accurate information on the distance dependence of resonance energy transfer (RET) is crucial for its utilization as a spectroscopic ruler \re{of} nanometer scale distances. In this regard, understanding the effects of donor-acceptor quantum coherence and non-Markovian bath, which become significant at short distances, has significant implications. The present work investigates this issue theoretically by comparing results from a theory of coherent RET (CRET) with a nonequilibrium version of Förster's RET (FRET) theory, both accounting for non-Markovian bath effects. Even for a model where the donor-acceptor electronic coupling is of transition dipole interaction form, it is shown that the RET rate in general deviates from the inverse sixth power distance dependence as opposed to the prediction of the original FRET. It is shown that the donor-acceptor quantum coherence makes the \re{distance} dependence steeper than the sixth power although detailed manner of enhancement is sensitive to specific values of parameters. On the other hand, the non-Markovian bath effects make the \re{distance} dependence more moderate than the sixth power for both CRET and nonueqilibrium FRET because finite time scale of the bath causes the rate to be smaller than the prediction of original FRET. While these effects are \re{demonstrated clearly} in the population dynamics at sub-picosecond time scales, their contributions to the conventional RET efficiency are relatively minor. This indicates that the actual detection of such effects through conventional RET efficiency measurement requires either high precision or utilization of a donor with fast spontaneous decay rate of excitation.

quant-ph↗

arXiv2026

Multistep quantum master equation theory for response functions in four wave mixing electronic spectroscopy of multichromophoric macromolecules

This work provides an alternative derivation of third order response functions in four wave mixing spectroscopy of multichromophoric macromolecular systems considering only single exciton states. For the case of harmonic oscillator bath linearly and diagonally coupled to exciton states, closed form expressions showing all the explicit time dependences are derived. These expressions can provide more solid physical basis for understanding 2-dimensional electronic spectroscopy signals. For more general cases of system-bath coupling, the quantum master equation (QME) approach is employed for the derivation of multistep time evolution equations for Green function-like operators. Solution of these equations is feasible at the level of 2nd order non-Markovian QME, and the new approach can account for inter-exciton coupling, dephasing, relaxation, and non-Markovian effects in a consistent manner.

quant-ph↗

arXiv2025

Simple and general unitarity conserving numerical real time propagators of time dependent Schrödinger equation based on Magnus expansion

Magnus expansion (ME) provides a general way to expand the real-time propagator of a time-dependent Hamiltonian within the exponential such that the unitarity is satisfied at any order. We use this property and explicit integration of Lagrange interpolation formulas for the time-dependent Hamiltonian within each time interval and derive approximations that preserve unitarity for the differential time evolution operators of general time-dependent Hamiltonians. The resulting second-order approximation is the same as using the average of Hamiltonians for two end points of time. We identify three fourth-order approximations involving commutators of Hamiltonians at different times and also derive a sixth-order expression. A test of these approximations along with other available expressions for a two-state time-dependent Hamiltonian with sinusoidal time dependences provides information on the relative performance of these approximations and suggests that the derived expressions can serve as useful numerical tools for time evolution in time-resolved spectroscopy, quantum control, quantum sensing, real-time ab initio quantum dynamics, and open system quantum dynamics.

quant-ph↗

arXiv2025

Nonadiabatic derivative couplings through multiple Franck-Condon modes dictate the energy gap law for near and short-wave infrared dye molecules

Near infrared (NIR, 700 - 1,000 nm) and short-wave infrared (SWIR, 1,000 - 2,000 nm) dye molecules exhibit significant nonradiative decay rates from the first singlet excited state to the ground state. While these trends can be empirically explained by a simple energy gap law, detailed mechanisms of the nearly universal behavior have remained unsettled for many cases. Theoretical and experimental results for two representative NIR/SWIR dye molecules reported here clarify the key mechanism for the observed energy gap law behavior. It is shown that the first derivative nonadiabatic coupling terms serve as major coupling pathways for nonadiabatic decay processes from the first excited singlet state to the ground state for these NIR and SWIR dye molecules and that vibrational modes other than the highest frequency ones also make significant contributions to the rate. This assessment is corroborated by further theoretical comparison with possible alternative mechanisms of intersystem crossing to triplet states and also by comparison with experimental data for deuterated molecules.

physics.chem-ph↗

arXiv2025

A simple generalization of the energy gap law for nonradiative processes

For more than 50 years, an elegant energy gap (EG) law developed by Englman and Jortner [Mol. Phys. {\bf 18}, 145 (1970)] has served as a key theory to understand and model nearly exponential dependence of nonradiative transition rates on the difference of energy between the initial and final states. This work revisits the theory, clarifies key assumptions involved in the rate expression, and provides a generalization for the cases where the effects of temperature dependence and low frequency modes cannot be ignored. For a specific example where the low frequency vibrational and/or solvation responses can be modeled as an Ohmic spectral density, a simple generalization of the EG law is provided. Test calculations demonstrate that this generalized EG law brings significant improvement over the original EG law. Both the original and generalized EG laws are also compared with stationary phase approximations developed for electron transfer theory, which suggests the possibility of a simple interpolation formula valid for any value of EG.

quant-ph↗

arXiv2025

Excitons: Energetics and spatio-temporal dynamics

The concept of an exciton as a quasiparticle that represents collective excited states was originally adapted from solid-state physics and has been successfully applied to molecular aggregates by relying on the well-established limits of the Wannier exciton and the Frenkel exciton. However, the study of excitons in more complex chemical systems and solid materials over the past two decades has made it clear that simple concepts based on Wannier or Frenkel excitons are not sufficient to describe detailed excitonic behavior, especially in nano-structured solid materials, multichromophoric macromolecules, and complex molecular aggregates. In addition, important effects such as vibronic coupling, the influence of charge-transfer (CT) components, spin-state interconversion, and electronic correlation, which had long been studied but not fully understood, have turned out to play a central role in many systems. This has motivated new experimental approaches and theoretical studies of increasing sophistication. This article provides an overview of works addressing these issues that were published for A Special Topic of the Journal of Chemical Physics on "Excitons: Energetics and spatio-temporal dynamics" and discusses their implications.

physics.chem-ph↗

arXiv2025

Partially polaron-transformed quantum master equation for exciton and charge transport dynamics

Polaron-transformed quantum master equation (PQME) offers a unified framework to describe the dynamics of quantum systems in both limits of weak and strong couplings to environmental degrees of freedom. Thus, PQME serves as an efficient method to describe charge and exciton transfer/transport dynamics for a broad range of parameters in condensed or complex environments. However, in some cases, the polaron transformation (PT) being employed in the formulation invokes an over-relaxation of slow modes and results in premature suppression of important coherence terms. A formal framework to address this issue is developed in the present work by employing a partial PT that has smaller weights for low frequency bath modes. It is shown here that a closed form expression of a 2nd order time-local PQME including all the inhomogeneous terms can be derived for a general form of partial PT, although more complicated than that for the full PT. All the expressions needed for numerical calculation are derived in detail. Applications to a model of two-level system coupled to a bath of harmonic oscillators, with test calculations focused on those due to homogeneous relaxation terms, demonstrate the feasibility and the utility of the present approach.

quant-ph↗

arXiv2025

Fermi's golden rule rate expression for transitions due to nonadiabatic derivative couplings in the adiabatic basis

Starting from a general molecular Hamiltonian expressed in the basis of adiabatic electronic and nuclear position states, where a compact and complete expression for nonadiabatic derivative coupling (NDC) Hamiltonian term is obtained, we provide a general analysis of the Fermi's golden rule (FGR) rate expression for nonadiabatic transitions between adiabatic states. We then consider a quasi-adiabatic approximation that uses crude adiabatic states evaluated at the minimum potential energy configuration of the initial adiabatic state as the basis for the zeroth order adiabatic and NDC coupling terms of the Hamiltonian. Although application of this approximation is rather limited, it allows deriving a general FGR rate expression without further approximation and still accounts for non-Condon effect arising from momentum operators of NDC terms and its coupling with vibronic displacements. For a generic and widely used model where all nuclear degrees of freedom and environmental effects are represented as linearly coupled harmonic oscillators, we derive a closed form FGR rate expression that requires only Fourier transform. The resulting rate expression includes quadratic contributions of NDC terms and their couplings to Franck-Condon modes, which require evaluation of two additional bath spectral densities in addition to conventional one that appears in a typical FGR rate theory based on the Condon approximation. Model calculations for the case where nuclear vibrations consist of both a sharp high frequency mode and an Ohmic bath spectral density illustrate new features and implications of the rate expression. We then apply our theoretical expression to the nonradiative decay from the first excited singlet state of azulene, which illustrates the utility and implications of our theoretical results.

quant-ph↗

arXiv2025

Modified Fermi's golden rule rate expressions

Fermi's golden rule (FGR) serves as the basis for many expressions of spectroscopic observables and quantum transition rates. The utility of FGR has been demonstrated through decades of experimental confirmation. However, there still remain important cases where the evaluation of a FGR rate is ambiguous or ill-defined. Examples are cases where the rate has divergent terms due to the sparsity in the density of final states or time dependent fluctuations of system Hamiltonians. Strictly speaking, assumptions of FGR are no longer valid for such cases. However, it is still possible to define modified FGR rate expressions that are useful as effective rates. The resulting modified FGR rate expressions resolve a long standing ambiguity often encountered in using FGR and offer more reliable ways to model general rate processes. Simple model calculations illustrate the utility and implications of new rate expressions.

quant-ph↗