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1. Exciton-Assisted Relaxation of Hot Carriers in Semiconductor Quantum Dots

   https://doi.org/10.1149/MA2024-01231396mtgabs  

   Griffin, Hadassah B; Kryjevski, Andrei B; Kilina, Svetlana V; Kilin, Dmitri S (August 2024, ECS Meeting Abstracts)

   The work provides computational arguments in support of excitonic approach for the treatment of the photo-induced processes in semiconductor quantum dots. The non-radiative relaxation, non-radiative recombination, and photo-luminescence quantum yield are computed for a range of atomistic models of semiconductor quantum dots (QDs) in the quantum confinement regime. The excitonic (EX) approach is compared to independent orbital approximation (IOA) approach. Both approaches address dissipation of the electronic energy from electronic degrees of freedom to thermal vibrations of the lattice. The difference of two approaches appears in treatment of energies of electronic states and in a way how the electron-phonon interaction is taken into account. IOA approach uses energies of Kohn-Sham orbitals and on the fly non-adiabatic couplings. [1-3] EX approach uses Bethe-Salpeter equation (BSE) for energies.[4-6] The excitonic wavefunctions from BSE is used to construct a linear transformation matrix that transforms IOA-based non-adiabatic couplings into an excitonic basis. Both approaches are compared in application to untrasmall 1 nm diameter Si QD.Results include an evidence that hot excitons relax sooner in the excitonic picture than in the IOA picture. The observed effect is rationalized via smaller subgaps and different available relaxation pathways in the excitonic picture. The most surprising result is found for the simulated emission spectrum. The spectum in the excitonic picture demonstrates intensity in several 5 orders of magnitude higher than in the IOA picture. This observation is related to formation of a bright exciton in the lowest excitation of the ultra-small Si QDs. Obtained evidence favors excitonic approach and promises a reliable interpretation and prediction of time-dependent observables in a range of semiconductor quantum dots of different composition, sizes, and surface environment.[7] Most intriguing results are expected for QDs representing interface between PbSe and CdSe. [8] Support of National Science foundation via NSF CHE-2004197 is gratefully acknowledged. [1] D. S. Kilin and D. A. Micha, “Relaxation of photoexcited electrons at a nanostructured Si(111) surface”, J. Phys. Chem. Lett. 1, 1073-1077 (2010). [2] D. J. Vogel and D. S. Kilin, "First-Principles Treatment of Photoluminescence in Semiconductors" J. Phys. Chem. C 119, 50, 27954–27964 (2015). [3] D. J. Vogel, A. B. Kryjevski, T. M. Inerbaev, and D. S. Kilin, "Photoinduced Single- and Multiple-Electron Dynamics Processes Enhanced by Quantum Confinement in Lead Halide Perovskite Quantum Dots", J. Phys. Chem. Lett. 8, 13, 3032–3039(2017). [4] A. B. Kryjevski and Dmitri Kilin, "Enhanced multiple exciton generation in amorphous silicon nanowires and films", Molec. Phys. 114, 365-379 (2016). [5] M. Rohlfing and S. G. Louie, "Electron-Hole Excitations in Semiconductors and Insulators", Phys. Rev. Lett. 81, 2312-2315 (1998). [6] T. Sander, G. Kresse, "Macroscopic dielectric function within time-dependent density functional theory—Real time evolution versus the Casida approach", J. Chem. Phys. 146, 064110 (2017). [7] S. V. Kilina, P. K. Tamukong, and D. S. Kilin, "Surface Chemistry of Semiconducting Quantum Dots: Theoretical Perspectives", Acc. Chem. Res. 49, 10, 2127–2135 (2016). [8] H. B. Griffin, A. B. Kryjevski, and Dmitri S. Kilin, "Ab initio calculations of through-space and through-bond charge-transfer properties of interacting Janus-like PbSe and CdSe quantum dot heterostructures", Molec. Phys., e2273415 (2023). 

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2. Classical and nonclassical effects in surface hopping methodology for simulating coupled electronic-nuclear dynamics

   https://doi.org/10.1039/C9FD00042A  

   Martens, Craig C. (January 2019, Faraday Discussions)

   In this paper, we analyze the detailed quantum-classical behavior of two alternative approaches to simulating molecular dynamics with electronic transitions: the popular fewest switches surface hopping (FSSH) method, introduced by Tully in 1990 [Tully, \textit{J.~Chem.~Phys.}, 1990, \textbf{93}, 1061] and our recently developed quantum trajectory surface hopping (QTSH) method [Martens, \textit{J.~Phys.~Chem.~A}, 2019 \textbf{123}, 1110]. Both approaches employ an independent ensemble of trajectories that undergo stochastic transitions between electronic surfaces. The methods differ in their treatment of energy conservation, with FSSH imposing conservation of the classical kinetic plus potential energy by rescaling of the classical momenta when a surface hop occurs, while QTSH incorporates quantum forces throughout the dynamics which lead naturally to the conservation of the full quantum-classical energy. We investigate the population transfer and energy budget of the surface hopping methods for several simple model systems and compare with exact quantum result. In addition, the detailed dynamics of the trajectory ensembles in phase space are compared with the quantum evolution in the Wigner representation. Conclusions are drawn. 

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3. Efficient, nonparametric removal of noise and recovery of probability distributions from time series using nonlinear-correlation functions: Photon and photon-counting noise

   https://doi.org/10.1063/5.0212157  

   Dhar, Mainak; Berg, Mark A (July 2024, The Journal of Chemical Physics)

   A preceding paper [M. Dhar, J. A. Dickinson, and M. A. Berg, J. Chem. Phys. 159, 054110 (2023)] shows how to remove additive noise from an experimental time series, allowing both the equilibrium distribution of the system and its Green’s function to be recovered. The approach is based on nonlinear-correlation functions and is fully nonparametric: no initial model of the system or of the noise is needed. However, single-molecule spectroscopy often produces time series with either photon or photon-counting noise. Unlike additive noise, photon noise is signal-size correlated and quantized. Photon counting adds the potential for bias. This paper extends noise-corrected-correlation methods to these cases and tests them on synthetic datasets. Neither signal-size correlation nor quantization is a significant complication. Analysis of the sampling error yields guidelines for the data quality needed to recover the properties of a system with a given complexity. We show that bias in photon-counting data can be corrected, even at the high count rates needed to optimize the time resolution. Using all these results, we discuss the factors that limit the time resolution of single-molecule spectroscopy and the conditions that would be needed to push measurements into the submicrosecond region. 

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4. Understanding dynamics in coarse-grained models. V. Extension of coarse-grained dynamics theory to non-hard sphere systems

   https://doi.org/10.1063/5.0254388  

   Jin, Jaehyeok; Voth, Gregory A (March 2025, The Journal of Chemical Physics)

   Coarse-grained (CG) modeling has gained significant attention in recent years due to its wide applicability in enhancing the spatiotemporal scales of molecular simulations. While CG simulations, often performed with Hamiltonian mechanics, faithfully recapitulate structural correlations at equilibrium, they lead to ambiguously accelerated dynamics. In Paper I [J. Jin, K. S. Schweizer, and G. A. Voth, J. Chem. Phys. 158(3), 034103 (2023)], we proposed the excess entropy scaling relationship to understand the CG dynamics. Then, in Paper II [J. Jin, K. S. Schweizer, and G. A. Voth, J. Chem. Phys. 158(3), 034104 (2023)], we developed a theory to map the CG system into a dynamically consistent hard sphere system to analytically derive an expression for fast CG dynamics. However, many chemical and physical systems do not exhibit hard sphere-like behavior, limiting the extensibility of the developed theory. In this paper, we aim to generalize the theory to the non-hard sphere system based on the Weeks–Chandler–Andersen perturbation theory. Since non-hard sphere-like CG interactions affect the excess entropy term as it deviates from the hard sphere description, we explicitly account for the extra entropy to correct the non-hard sphere nature of the system. This approach is demonstrated for two different types of interactions seen in liquids, and we further provide a generalized description for any CG models using the generalized Gaussian CG models using Gaussian basis sets. Altogether, this work allows for extending the range and applicability of the hard sphere CG dynamics theory to a myriad of CG liquids. 

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5. Particle paths in nonlinear Schrödinger models in the presence of linear shear currents

   https://doi.org/10.1017/jfm.2018.623  

   Curtis, C. W.; Carter, J. D.; Kalisch, H. (November 2018, Journal of Fluid Mechanics)

   We investigate the effect of constant-vorticity background shear on the properties of wavetrains in deep water. Using the methodology of Fokas ( A Unified Approach to Boundary Value Problems , 2008, SIAM), we derive a higher-order nonlinear Schrödinger equation in the presence of shear and surface tension. We show that the presence of shear induces a strong coupling between the carrier wave and the mean-surface displacement. The effects of the background shear on the modulational instability of plane waves is also studied, where it is shown that shear can suppress instability, although not for all carrier wavelengths in the presence of surface tension. These results expand upon the findings of Thomas et al.  ( Phys. Fluids , vol. 24 (12), 2012, 127102). Using a modification of the generalized Lagrangian mean theory in Andrews & McIntyre ( J. Fluid Mech. , vol. 89, 1978, pp. 609–646) and approximate formulas for the velocity field in the fluid column, explicit, asymptotic approximations for the Lagrangian and Stokes drift velocities are obtained for plane-wave and Jacobi elliptic function solutions of the nonlinear Schrödinger equation. Numerical approximations to particle trajectories for these solutions are found and the Lagrangian and Stokes drift velocities corresponding to these numerical solutions corroborate the theoretical results. We show that background currents have significant effects on the mean transport properties of waves. In particular, certain combinations of background shear and carrier wave frequency lead to the disappearance of mean-surface mass transport. These results provide a possible explanation for the measurements reported in Smith ( J. Phys. Oceanogr. , vol. 36, 2006, pp. 1381–1402). Our results also provide further evidence of the viability of the modification of the Stokes drift velocity beyond the standard monochromatic approximation, such as recently proposed in Breivik et al.  ( J. Phys. Oceanogr. , vol. 44, 2014, pp. 2433–2445) in order to obtain a closer match to a range of complex ocean wave spectra. 

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