arXiv subjects

Yoshitaka Tanimura

Publications and source records attributed to Yoshitaka Tanimura.

At least 55 records · Page 3Linked to original sources

arXiv2019

Phase-space wavepacket dynamics of internal conversion via conical intersection: Multi-state quantum Fokker-Planck equation approach

We theoretically investigate internal conversion processes of a photoexcited molecule in a condensed phase. The molecular system is described by two-dimensional adiabatic ground and excited potential energy surfaces (PESs) that are coupled to heat baths. We study the role of conical intersection (CI) by computing the time evolution of wavepackets for the PESs both with and without the CI. For this purpose, we employ the multi-state quantum Fokker-Planck equation (MSQFPE) for a two-dimensional Wigner space. Numerically integrating the MSQFPE, we investigated the time evolution of wavepackets for the CI and avoided crossing (AC) models. We find that the calculated yields through non-adiabatic transitions are sensitive to the profile of the PESs of the CI model: Due to the vibrational motion in the coupling mode, the yield depends on the distance between the CI point and the minimum point of the adiabatic excited-state PES.

physics.chem-ph↗

arXiv2019

Probing photoisomerization processes by means of multi-dimensional electronic spectroscopy: The multi-state quantum hierarchical Fokker-Planck equation approach

Photoisomerization in a system with multiple electronic states and anharmonic potential surfaces in a dissipative environment is investigated using a rigorous numerical method employing quantum hierarchical Fokker-Planck equations (QHFPE) for multi-state systems. We have developed a computer code incorporating QHFPE for general-purpose computing on graphics processing units (GPGPU) that can treat multi-state systems in phase space with any strength of diabatic coupling of electronic states under non-perturbative and non-Markovian system-bath interactions. This approach facilitates the calculation of both linear and nonlinear spectra. We computed Wigner distributions for excited, ground, and coherent states. We then investigated excited state dynamics involving transitions among these states by analyzing linear absorption and transient absorption processes and multi-dimensional electronic spectra with various values of the heat bath parameters. Our results provide predictions for spectroscopic measurements of photoisomerization dynamics. The motion of excitation and ground state wavepackets and their coherence involved in the photoisomerization were observed as the profiles of positive and negative peaks of two-dimensional spectra.

physics.chem-ph↗

arXiv2019

Modeling and analyzing a photo-driven molecular motor system: Ratchet dynamics and non-linear optical spectra

A light-driven molecular motor system is investigated using a multi-state Brownian ratchet model described by a single effective coordinate with multiple electronic states in a dissipative environment. The rotational motion of the motor system is investigated on the basis of wavepacket dynamics. A current determined from the interplay between a fast photochemical isomerization (photoisomerization) process triggered by pulses and a slow thermal isomerization (thermalization) process arising from an overdamped environment is numerically evaluated. For this purpose, we employ the multi-state low-temperature quantum Smoluchowski equations that allow us to simulate the fast quantum electronic dynamics in the overdamped environment. We analyze the motor efficiency by numerically integrating the equations of motion for a rotator system driven by repeatedly impulsive excitations. When the timescales of the pulse repetition, photoisomerization, and thermalization processes are separated, the average rotational speed of the motor is determined by the timescale of thermalization. In this regime, the average rotational current can be described by a simple equation derived from a rate equation for the thermalization process. When laser pulses are applied repeatedly and the timescales of the photoisomerization and pulse repetition are close, the details of the photoisomerization process become important to analyze the entire rotational process. We examine the possibility of observing the photoisomerization and the thermalization processes associated with stationary rotating dynamics of the motor system by spectroscopic means, e.g. pump-probe, transient absorption, and two-dimensional electronic spectroscopy techniques.

physics.chem-ph↗

arXiv2018

Linear Absorption Spectrum of a Quantum Two-Dimensional Rotator Calculated Using a Rotationally Invariant System-Bath Hamiltonian

We consider a two-dimensional rigid rotator system coupled to a two-dimensional heat bath. The Caldeira-Leggett (Brownian) model for the rotator and the spin-Boson model have been used to describe such systems, but they do not possess rotational symmetry, they cannot describe the discretized rotational bands in absorption and emission spectra that have been found experimentally. Here, to address this problem, we introduce a rotationally invariant system-bath (RISB) model that is described by two sets of harmonic-oscillator baths independently coupled to the rigid rotator as sine and cosine functions of the rotator angle. Due to a difference in the energy discretization of the total Hamiltonian, the dynamics described by the RISB model differ significantly from those described by the rotational Caldeira-Legget (RCL) model, while both models reduce to the Langevin equation for a rotator in the classical limit. To demonstrate this point, we compute the rotational absorption spectrum defined by the linear response function of a rotator dipole. For this purpose, we derive a quantum master equation for the RISB model in the high-temperature Markovian case. We find that the spectral profiles of the calculated signals exhibit a transition from quantized rotational bands to a single peak after spectrum collapse. This is a significant finding, because previous approaches cannot describe such phenomena in a unified manner.

cond-mat.stat-mech↗

arXiv2018

Hierarchical Schrödinger Equations of Motion for Open Quantum Dynamics

We rigorously investigate the quantum non-Markovian dissipative dynamics of a system coupled to a harmonic oscillator bath by deriving hierarchical Schrodinger equations of motion (HSEOM) and studying their dynamics. The HSEOM are the equations for wave functions derived on the basis of the Feynman-Vernon influence functional formalism for the density operator, $\langle q|ρ(t)|q' \rangle$, where $\langle q|$ and $|q' \rangle$ are the left- and right-hand elements. The time evolution of $\langle q|$ is computed from time $0$ to $t$, and subsequently, the time evolution of $|q' \rangle$ is computed from time $t$ to $0$ along a contour in the complex time plane. By appropriately choosing functions for the bath correlation function and the spectral density, we can take advantage of an HSEOM method to carry out simulations without the need for a great amount of computational memory. As a demonstration, quantum annealing simulation for a ferromagnetic $p$-spin model is studied.

quant-ph↗

arXiv2018

Hierarchical Equations of Motion Approach to Quantum Thermodynamics

We present a theoretical framework to investigate quantum thermodynamic processes under non-Markovian system-bath interactions on the basis of the hierarchical equations of motion (HEOM) approach, which is convenient to carry out numerically "exact" calculations. This formalism is valuable because it can be used to treat not only strong system-bath coupling but also system-bath correlation or entanglement, which will be essential to characterize the heat transport between the system and quantum heat baths. Using this formalism, we demonstrated an importance of the thermodynamic effect from the tri-partite correlations (TPC) for a two-level heat transfer model and a three-level autonomous heat engine model under the conditions that the conventional quantum master equation approaches are failed. Our numerical calculations show that TPC contributions, which distinguish the heat current from the energy current, have to be take into account to satisfy the thermodynamic laws.

quant-ph↗

arXiv2017

Quantum Heat Current under Non-perturbative and Non-Markovian Conditions: Applications to Heat Machines

We consider a quantum system strongly coupled to multiple heat baths at different temperatures. Quantum heat transport phenomena in this system are investigated using two definitions of the heat current, one in terms of the system energy, and the other in terms of the bath energy. When we consider correlations among system-bath interactions (CASBI) -- which have a purely quantum mechanical origin -- the definition in terms of the bath energy becomes different. We found that CASBI are necessary to maintain the consistency of the heat current with thermodynamic laws in the case of strong system-bath coupling. However, within the context of the quantum master equation approach, both of these definitions are identical. Through a numerical investigation, we demonstrate this point for a non-equilibrium spin-boson model and a three-level heat engine model using the reduced hierarchal equations of motion approach under strongly coupled and non-Markovian conditions. We observe cyclic behavior of the heat currents and the work performed by the heat engine,and we find that their phases depend on the system-bath coupling strength. Through consideration of the bath heat current, we show that the efficiency of the heat engine decreases as the strength of the system-bath coupling increases, due to the CASBI contribution. In the case of a large system-bath coupling, the efficiency increases further if the bath temperature is decreased, with fixed the ratio of the bath temperatures, due to the discretized nature of energy eigenstates. This is also considered to be a unique feature of quantum heat engines.

quant-ph↗

arXiv2017

An exciton-coupled electron transfer process controlled by non-Markovian environments

We theoretically investigate an exciton-coupled electron transfer (XCET) process that is conversion of an exciton into a charge transfer state. This conversion happens in an exciton transfer (XT) process, and the electron moves away in an electron transfer(ET) process in multiple environments (baths). This XCET process plays an essential role in the harvesting of solar energy in biological and photovoltaic materials. We develop a practical theoretical model to study the efficiency of XCET process that occurs either in consecutive or concerted processes under the influence of non-Markovian baths. The role of quantum coherence in the XT-ET system and the baths is investigated using reduced hierarchal equations of motion (HEOM). This model includes independent baths for each XT and ET state, in addition to a XCET bath for the conversion process. We found that, while quantum system-bath coherence is important in the XT and ET processes, coherence between the XT and ET processes must be suppressed in order to realize efficient irreversible XCET process through the weak off-diagonal interaction between the XT and ET bridge sites arises from a XCET bath.

quant-ph↗

arXiv2016

Exploring complete positivity in hierarchy equations of motion

We derive a purely algebraic framework for the identification of hierarchy equations of motion that induce completely positive dynamics and demonstrate the applicability of our approach with several examples. We find bounds on the violation of complete positivity for microscopically derived hierarchy equations of motion and construct well-behaved phenomenological models with strongly non-Markovian revivals of quantum coherence.

quant-ph↗

arXiv2016

Full molecular dynamics simulations of liquid water and carbon tetrachloride for two-dimensional Raman spectroscopy in the frequency domain

Frequency-domain two-dimensional Raman signals, which are equivalent to coherent two-dimensional Raman scattering (COTRAS) signals, for liquid water and carbon tetrachloride were calculated using an equilibrium-nonequilibrium hybrid MD simulation algorithm. We elucidate mechanisms governing the 2D signal profiles involving anharmonic mode-mode coupling and the nonlinearities of the polarizability for the intermolecular and intramolecular vibrational modes. The predicted signal profiles and intensities can be utilized to analyze recently developed single-beam 2D spectra, whose signals are generated from a coherently controlled pulse, allowing the single-beam measurement to be carried out more efficiently.

physics.chem-ph↗

arXiv2015

Analysis of 2D THz-Raman spectroscopy using a non-Markovian Brownian oscillator model with nonlinear system-bath interactions

We explore and describe the roles of inter-molecular vibrations employing a Brownian oscillator (BO) model with linear-linear (LL) and square-linear (SL) system-bath interactions, which we use to analyze two-dimensional (2D) THz-Raman spectra obtained by means of molecular dynamics (MD) simulations. In addition to linear absorption (1D IR), we calculated 2D Raman-THz-THz, THz-Raman-THz, and THz-THz-Raman signals for liquid formamide, water, and methanol using an equilibrium non-equilibrium hybrid MD simulation. The calculated 1D IR and 2D THz-Raman signals are compared with results obtained from the LL+SL BO model applied through use of hierarchal Fokker-Planck equations with non-perturbative and non-Markovian noise. We find that all of the qualitative features of the 2D profiles of the signals obtained from the MD simulations are reproduced with the LL+SL BO model, indicating that this model captures the essential features of the inter-molecular motion. We analyze the fitted 2D profiles in terms of anharmonicity, nonlinear polarizability, and dephasing time. The origins of the echo peaks of the librational motion and the elongated peaks parallel to the probe direction are elucidated using optical Liouville paths.

physics.chem-ph↗

arXiv2015

Real-Time and Imaginary-Time Quantum Hierarchal Fokker-Planck Equations

We consider a quantum mechanical system represented in phase space (referred to hereafter as "Wigner space"), coupled to a harmonic oscillator bath. We derive quantum hierarchal Fokker-Planck (QHFP) equations not only in real time, but also in imaginary time, which represents an inverse temperature. This is an extension of a previous work, in which we studied a spin-boson system, to a Brownian system. It is shown that the QHFP in real time obtained from a correlated thermal equilibrium state of the total system possess the same form as those obtained from a factorized initial state. A modified terminator for the hierarchal equations of motion is introduced to treat the non-Markovian case more efficiently. Using the imaginary-time QHFP, numerous thermodynamic quantities, including the free energy, entropy, internal energy, heat capacity, and susceptibility can be evaluated for any potential. These equations allow us to treat non-Markovian, non-perturbative system-bath interactions at finite temperature. Through numerical integration of the real-time QHFP for a harmonic system, we obtain the equilibrium distributions, the auto-correlation function, and the first- and second-order response functions. These results are compared with analytically exact results for the same quantities. This provides a critical test of the formalism for a non-factorized thermal state, and elucidates the roles of fluctuation, dissipation, non-Markovian effects, and system-bath coherence. Employing numerical solutions of the imaginary-time QHFP, we demonstrate the capability of this method to obtain thermodynamic quantities for any potential surface. It is shown that both types of QHFP equations can produce numerical results of any desired accuracy.

cond-mat.stat-mech↗

arXiv2015

Linear, third- and fifth-order nonlinear spectroscopy of a charge transfer system coupled to an underdamped vibration

We study hole, electron and exciton transport in a charge transfer system in the presence of underdamped vibrational motion. We analyze the signature of these processes in the linear and third-, and fifth-order nonlinear electronic spectra. Calculations are performed with a numerically exact hierarchical equations of motion method for an underdamped Brownian oscillator spectral density. We find that combining electron, hole and exciton transfer can lead to non-trivial spectra with more structure than with excitonic coupling alone. Traces taken during the waiting time of a two-dimensional spectrum are dominated by vibrational motion and do not reflect the electron, hole, and exciton dynamics directly. We find that the fifth-order nonlinear response is particularly sensitive to the charge transfer process. While third-order 2D spectroscopy detects the correlation between two coherences, fifth-order 2D spectroscopy (2D population spectroscopy) is here designed to detect correlations between the excited states during two different time periods.

physics.chem-ph↗

arXiv2015

Reduced hierarchical equations of motion in real and imaginary time: Correlated initial states and thermodynamic quantities

For a system strongly coupled to a heat bath, the quantum coherence of the system and the heat bath plays an important role in the system dynamics. This is particularly true in the case of non-Markovian noise. We rigorously investigate the influence of system-bath coherence by deriving the reduced hierarchal equations of motion (HEOM), not only in real time, but also in imaginary time, which represents an inverse temperature. It is shown that the HEOM in real time obtained when we include the system-bath coherence of the initial thermal equilibrium state possess the same form as those obtained from a factorized initial state. We find that the difference in behavior of systems treated in these two manners results from the difference in initial conditions of the HEOM elements, which are defined in path integral form. We also derive HEOM along the imaginary time path to obtain the thermal equilibrium state of a system strongly coupled to a non-Markovian bath. Then, we show that the steady state hierarchy elements calculated from the real-time HEOM can be expressed in terms of the hierarchy elements calculated from the imaginary-time HEOM. Moreover, we find that the imaginary-time HEOM allow us to evaluate a number of thermodynamic variables, including the free energy, entropy, internal energy, heat capacity, and susceptibility. The expectation values of the system energy and system-bath interaction energy in the thermal equilibrium state are also evaluated.

cond-mat.stat-mech↗

arXiv2013

Self-excited current oscillations in a resonant tunneling diode described by a model based on the Caldeira-Leggett Hamiltonian

The quantum dissipative dynamics of a tunneling process through double barrier structures is investigated on the basis of non-perturbative and non-Markovian treatment. We employ a Caldeira-Leggett Hamiltonian with an effective potential calculated self-consistently, accounting for the electron distribution. With this Hamiltonian, we use the reduced hierarchy equations of motion in the Wigner space representation to study non-Markovian and non-perturbative thermal effects at finite temperature in a rigorous manner. We study current variation in time and the current-voltage (I-V) relation of the resonant tunneling diode for several widths of the contact region, which consists of doped GaAs. Hysteresis and both single and double plateau-like behavior are observed in the negative differential resistance (NDR) region. While all of the current oscillations decay in time in the NDR region in the case of a strong system-bath coupling, there exist self-excited high-frequency current oscillations in some parts of the plateau in the NDR region in the case of weak coupling. We find that the effective potential in the oscillating case possesses a basin-like form on the emitter side (emitter basin) and that the current oscillation results from tunneling between the emitter basin and the quantum well in the barriers. We find two distinct types of current oscillations, with large and small oscillation amplitudes, respectively. These two types of oscillation appear differently in the Wigner space, with one exhibiting tornado-like motion and the other exhibiting a two piston engine-like motion.

cond-mat.mes-hall↗

arXiv2013

Quantum Suppression of Ratchet Rectification in a Brownian System Driven by a Biharmonic Force

We rigorously investigate the quantum dissipative dynamics of a ratchet system described by a periodic potential model based on the Caldeira-Leggett Hamiltonian with a biharmonic force. In this model, we use the reduced hierarchy equations of motion in the Wigner space representation. These equations represent a generalization of the Gaussian-Markovian quantum Fokker-Planck equation introduced by Tanimura and Wolynes (1991), which was formulated to study non-Markovian and non-perturbative thermal effects at finite temperature. This formalism allows us to treat both the classical limit and the tunneling regimes, and it is helpful for identifying purely quantum mechanical effects through the time evolution of the Wigner distribution. We carried out extensive calculations of the classical and quantum currents for various temperatures, coupling strengths, and barrier heights. Our results reveal that at low temperature, while the quantum current is larger than the classical current in the case of a high barrier, the opposite is true in the case of a low barrier. We find that this behavior results from the fact that the tunneling enhances the current in the case of a high barrier, while it suppresses the current in the case of a low barrier. This is because the effect of the ratchet potential is weak in the case of a low barrier, due to the large dispersion of the distribution introduced by tunneling. This causes the spatio-temporal asymmetry, which is necessary for ratchet current, to be weak, and as a result, the net current is suppressed.

quant-ph↗

arXiv2013

An approach to quantum transport based on reduced hierarchy equations of motion: Application to a resonant tunneling diode

The quantum dissipative dynamics of a tunneling process through double barrier structures is investigated on the basis of a rigorous treatment for the first time. We employ a Caldeira-Leggett Hamiltonian with an effective potential calculated self-consistently, accounting for the electron distribution. With this Hamiltonian, we use the reduced hierarchy equations of motion in the Wigner space representation to study the effects of non-Markovian thermal fluctuations and dissipation at finite temperature in a rigorous manner. Hysteresis, double plateau-like behavior, and self-excited current oscillation are observed in a negative differential resistance (NDR) region of the current-voltage curve. We find that while most of the current oscillations decay in time in the NDR region, there is a steady oscillation characterized by a tornado-like rotation in the Wigner space in the upper plateau of the NDR region.

cond-mat.mes-hall↗

arXiv2012

Reduced hierarchy equations of motion approach with Drude plus Brownian spectral distribution: Probing electron transfer processes by means of two- dimensionalcorrelation spectroscopy

We theoretically investigate an electron transfer (ET) process in a dissipative environment by means of two-dimensional (2D) correlation spectroscopy. We extend the reduced hierarchy equations of motion approach to include both overdamped Drude and underdamped Brownian modes. While the overdamped mode describes the inhomogeneity of a system in the slow modulation limit, the underdamped mode expresses the primary vibrational mode coupled with the electronic states. We outline a procedure for calculating 2D correlation spectrum that incorporates the ET processes. The present approach has the capability of dealing with system-bath coherence under an external perturbation, which is important to calculate nonlinear response functions for non-Markovian noise. The calculated 2D spectrum exhibits the effects of the ET processes through the presence of ET transition peaks along the $Ω_1$ axis, as well as the decay of echo signals.

physics.chem-ph↗