All Publications
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2D spectroscopies from condensed phase dynamics: Accessing third-order response properties from equilibrium multi-time correlation functions.
The Journal of chemical physics
2022; 157 (9): 094111
Abstract
The third-order response lies at the heart of simulating and interpreting nonlinear spectroscopies ranging from two-dimensional infrared (2D-IR) to 2D electronic (2D-ES), and 2D sum frequency generation (2D-SFG). The extra time and frequency dimensions in these spectroscopic techniques provide access to rich information on the electronic and vibrational states present, the coupling between them, and the resulting rates at which they exchange energy that are obscured in linear spectroscopy, particularly for condensed phase systems that usually contain many overlapping features. While the exact quantum expression for the third-order response is well established, it is incompatible with the methods that are practical for calculating the atomistic dynamics of large condensed phase systems. These methods, which include both classical mechanics and quantum dynamics methods that retain quantum statistical properties while obeying the symmetries of classical dynamics, such as LSC-IVR, centroid molecular dynamics, and Ring Polymer Molecular Dynamics (RPMD), naturally provide short-time approximations to the multi-time symmetrized Kubo transformed correlation function. Here, we show how the third-order response can be formulated in terms of equilibrium symmetrized Kubo transformed correlation functions. We demonstrate the utility and accuracy of our approach by showing how it can be used to obtain the third-order response of a series of model systems using both classical dynamics and RPMD. In particular, we show that this approach captures features such as anharmonically induced vertical splittings and peak shifts while providing a physically transparent framework for understanding multidimensional spectroscopies.
View details for DOI 10.1063/5.0107087
View details for PubMedID 36075710
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Optimal linear cyclic quantum heat engines cannot benefit from strong coupling.
Physical review. E
2022; 106 (2): L022105
Abstract
Uncovering whether strong system-bath coupling can be an advantageous operation resource for energy conversion can facilitate the development of efficient quantum heat engines (QHEs). Yet, a consensus on this ongoing debate is still lacking owing to challenges arising from treating strong couplings. Here, we conclude the debate for optimal linear cyclic QHEs operated under a small temperature difference by revealing the detrimental role of strong system-bath coupling in their optimal operations. We analytically demonstrate that both the efficiency at maximum power and maximum efficiency of strong-coupling linear cyclic QHEs are upper bounded by their weak-coupling counterparts with the same degree of time-reversal symmetry breaking. Under strong time-reversal symmetry breaking, we further reveal a quadratic suppression of the optimal efficiencies relative to the Carnot limit when away from the weak-coupling regime, along with a quadratic enhancement of the mean entropy production rate.
View details for DOI 10.1103/PhysRevE.106.L022105
View details for PubMedID 36109930
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Optically Induced Anisotropy in Time-Resolved Scattering: Imaging Molecular-Scale Structure and Dynamics in Disordered Media with Experiment and Theory.
Physical review letters
2022; 129 (5): 056001
Abstract
Time-resolved scattering experiments enable imaging of materials at the molecular scale with femtosecond time resolution. However, in disordered media they provide access to just one radial dimension thus limiting the study of orientational structure and dynamics. Here we introduce a rigorous and practical theoretical framework for predicting and interpreting experiments combining optically induced anisotropy and time-resolved scattering. Using impulsive nuclear Raman and ultrafast x-ray scattering experiments of chloroform and simulations, we demonstrate that this framework can accurately predict and elucidate both the spatial and temporal features of these experiments.
View details for DOI 10.1103/PhysRevLett.129.056001
View details for PubMedID 35960558
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Periodically Driven Quantum Thermal Machines from Warming up to Limit Cycle.
Physical review letters
2021; 127 (20): 200602
Abstract
Theoretical treatments of periodically driven quantum thermal machines (PD-QTMs) are largely focused on the limit-cycle stage of operation characterized by a periodic state of the system. Yet, this regime is not immediately accessible for experimental verification. Here, we present a general thermodynamic framework that handles the performance of PD-QTMs both before and during the limit-cycle stage of operation. It is achieved by observing that periodicity may break down at the ensemble average level, even in the limit-cycle phase. With this observation, and using conventional thermodynamic expressions for work and heat, we find that a complete description of the first law of thermodynamics for PD-QTMs requires a new contribution, which vanishes only in the limit-cycle phase under rather weak system-bath couplings. Significantly, this contribution is substantial at strong couplings even at limit cycle, thus largely affecting the behavior of the thermodynamic efficiency. We demonstrate our framework by simulating a quantum Otto engine building upon a driven resonant level model. Our results provide new insights towards a complete description of PD-QTMs, from turn-on to the limit-cycle stage and, particularly, shed light on the development of quantum thermodynamics at strong coupling.
View details for DOI 10.1103/PhysRevLett.127.200602
View details for PubMedID 34860071
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Periodically Driven Quantum Thermal Machines from Warming up to Limit Cycle
PHYSICAL REVIEW LETTERS
2021; 127 (20)
View details for DOI 10.1103/PhysRevLett.127.200602
View details for Web of Science ID 000719465900005
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Ring-polymer, centroid, and mean-field approximations to multi-time Matsubara dynamics
JOURNAL OF CHEMICAL PHYSICS
2020; 153 (12): 124112
Abstract
Based on a recently developed generalization of Matsubara dynamics to the multi-time realm, we present a formal derivation of multi-time generalizations of ring-polymer molecular dynamics, thermostatted ring-polymer molecular dynamics (TRPMD), centroid molecular dynamics (CMD), and mean-field Matsubara dynamics. Additionally, we analyze the short-time accuracy of each methodology. We find that for multi-time correlation functions of linear operators, (T)RPMD is accurate up to order t3, while CMD is only correct up to t, indicating a degradation in the accuracy of these methodologies with respect to the single-time counterparts. The present work provides a firm justification for the use of path-integral-based approximations for the calculation of multi-time correlation functions.
View details for DOI 10.1063/5.0021843
View details for Web of Science ID 000577137700002
View details for PubMedID 33003707
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Energy transfer under natural incoherent light: Effects of asymmetry on efficiency
JOURNAL OF CHEMICAL PHYSICS
2020; 153 (11): 114102
Abstract
The non-equilibrium stationary coherences that form in donor-acceptor systems are investigated to determine their relationship to the efficiency of energy transfer to a neighboring reaction center. It is found that the effects of asymmetry in the dimer are generally detrimental to the transfer of energy. Four types of systems are examined, arising from combinations of localized trapping, delocalized (Forster) trapping, eigenstate dephasing, and site basis dephasing. In the cases of site basis dephasing, the interplay between the energy gap of the excited dimer states and the environment is shown to give rise to a turnover effect in the efficiency under weak dimer coupling conditions. Furthermore, the nature of the coherences and associated flux is interpreted in terms of pathway interference effects. In addition, regardless of the cases considered, the ratio of the real part and the imaginary part of the coherences in the energy-eigenbasis tends to a constant value in the steady state limit.
View details for DOI 10.1063/5.0020576
View details for Web of Science ID 000573433800002
View details for PubMedID 32962363
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Two-dimensional Raman spectroscopy of Lennard-Jones liquids via ring-polymer molecular dynamics
JOURNAL OF CHEMICAL PHYSICS
2020; 153 (3): 034117
Abstract
The simulation of multidimensional vibrational spectroscopy of condensed-phase systems including nuclear quantum effects is challenging since full quantum-mechanical calculations are still intractable for large systems comprising many degrees of freedom. Here, we apply the recently developed double Kubo transform (DKT) methodology in combination with ring-polymer molecular dynamics (RPMD) for evaluating multi-time correlation functions [K. A. Jung et al., J. Chem. Phys. 148, 244105 (2018)], providing a practical method for incorporating nuclear quantum effects in nonlinear spectroscopy of condensed-phase systems. We showcase the DKT approach in the simulation of the fifth-order two-dimensional (2D) Raman spectroscopy of Lennard-Jones liquids as a prototypical example, which involves nontrivial nonlinear spectroscopic observables of systems described by anharmonic potentials. Our results show that the DKT can faithfully reproduce the 2D Raman response of liquid xenon at high temperatures, where the system behaves classically. In contrast, liquid neon at low temperatures exhibits moderate but discernible nuclear quantum effects in the 2D Raman response compared to the responses obtained with classical molecular dynamics approaches. Thus, the DKT formalism in combination with RPMD simulations enables simulations of multidimensional optical spectroscopy of condensed-phase systems that partially account for nuclear quantum effects.
View details for DOI 10.1063/5.0015436
View details for Web of Science ID 000553907500006
View details for PubMedID 32716164
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Multi-time formulation of Matsubara dynamics
JOURNAL OF CHEMICAL PHYSICS
2019; 151 (3): 034108
Abstract
Matsubara dynamics has recently emerged as the most general form of a quantum-Boltzmann-conserving classical dynamics theory for the calculation of single-time correlation functions. Here, we present a generalization of Matsubara dynamics for the evaluation of multitime correlation functions. We first show that the Matsubara approximation can also be used to approximate the two-time symmetrized double Kubo transformed correlation function. By a straightforward extension of these ideas to the multitime realm, a multitime Matsubara dynamics approximation can be obtained for the multitime fully symmetrized Kubo transformed correlation function. Although not a practical method, due to the presence of a phase-term, this multitime formulation of Matsubara dynamics represents a benchmark theory for future development of Boltzmann preserving semiclassical approximations to general higher order multitime correlation functions. It also reveals a connection between imaginary time-ordering in the path integral and the classical dynamics of multitime correlation functions.
View details for DOI 10.1063/1.5110427
View details for Web of Science ID 000476588700034
View details for PubMedID 31325942
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Inclusion of nuclear quantum effects for simulations of nonlinear spectroscopy
JOURNAL OF CHEMICAL PHYSICS
2018; 148 (24): 244105
Abstract
The computation and interpretation of nonlinear vibrational spectroscopy is of vital importance for understanding a wide range of dynamical processes in molecular systems. Here, we introduce an approach to evaluate multi-time response functions in terms of multi-time double symmetrized Kubo transformed thermal correlation functions. Furthermore, we introduce a multi-time extension of ring polymer molecular dynamics to evaluate these Kubo transforms. Benchmark calculations show that the approximations are useful for short times even for nonlinear operators, providing a consistent improvement over classical simulations of multi-time correlation functions. The introduced methodology thus provides a practical way of including nuclear quantum effects in multi-time response functions of non-linear optical spectroscopy.
View details for DOI 10.1063/1.5036768
View details for Web of Science ID 000437190300053
View details for PubMedID 29960352
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Electron Transfer Assisted by Vibronic Coupling from Multiple Modes
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
2017; 13 (12): 6000–6009
Abstract
Understanding the effect of vibronic coupling on electron transfer (ET) rates is a challenge common to a wide range of applications, from electrochemical synthesis and catalysis to biochemical reactions and solar energy conversion. The Marcus-Jortner-Levich (MJL) theory offers a model of ET rates based on a simple analytic expression with a few adjustable parameters. However, the MJL equation in conjunction with density functional theory (DFT) has yet to be established as a predictive first-principles methodology. A framework is presented for calculating transfer rates modulated by molecular vibrations, that circumvents the steep computational cost which has previously necessitated approximations such as condensing the vibrational manifold into a single empirical frequency. Our DFT-MJL approach provides robust and accurate predictions of ET rates spanning over 4 orders of magnitude in the 106-1010 s-1 range. We evaluate the full MJL equation with a Monte Carlo sampling of the entire active space of thermally accessible vibrational modes, while using no empirical parameters. The contribution to the rate of individual modes is illustrated, providing insight into the interplay between vibrational degrees of freedom and changes in electronic state. The reported findings are valuable for understanding ET rates modulated by multiple vibrational modes, relevant to a broad range of systems within the chemical sciences.
View details for DOI 10.1021/acs.jctc.7b00513
View details for Web of Science ID 000418205100016
View details for PubMedID 29095611