Effect of conical intersection of benzene on non-adiabatic dynamics

The effect of conical intersection on the excited dynamics of benzene is studied by ab initio theory of electronic structure, which provides an important insight into photophysical and photochemical reactions. Based on the CASSCF(6,6)/6-31+G(d, p) method, the topological structures of conical intersections S₁/S and S₂/S₁ of benzene, as well as the optimal structures of the ground state (S) and excited states (S₁, S₂), are determined. The energy minima of the S₁ state and S₂ state are estimated at 4.608 eV and 6.889 eV, respectively. In addition, the energy values of the conical intersections of S₁/S and S₂/S₁ are predicted to be 5.600 eV and 6.774 eV. According to the topological structures and energy values of the S₂/S₁ and S₁/S conical intersections, the photophysical behavior of benzene excited to the S₂ state and the effects of the S₂/S₁ and S₁/S conical intersections are discussed in detail.     

Matrix Product State Simulations of Non-Equilibrium Steady States and Transient Heat Flows in the Two-Bath Spin-Boson Model at Finite Temperatures

Simulating the non-perturbative and non-Markovian dynamics of open quantum systems is a very challenging many body problem, due to the need to evolve both the system and its environments on an equal footing. Tensor network and matrix product states (MPS) have emerged as powerful tools for open system models, but the numerical resources required to treat finite-temperature environments grow extremely rapidly and limit their applications. In this study we use time-dependent variational evolution of MPS to explore the striking theory of Tamascelli et al. (Phys. Rev. Lett. 2019, 123, 090402.) that shows how finite-temperature open dynamics can be obtained from zero temperature, i.e., pure wave function, simulations. Using this approach, we produce a benchmark dataset for the dynamics of the Ohmic spin-boson model across a wide range of coupling strengths and temperatures, and also present a detailed analysis of the numerical costs of simulating non-equilibrium steady states, such as those emerging from the non-perturbative coupling of a qubit to baths at different temperatures. Despite ever-growing resource requirements, we find that converged non-perturbative results can be obtained, and we discuss a number of recent ideas and numerical techniques that should allow wide application of MPS to complex open quantum systems.     

Dissipation-Induced Information Scrambling in a Collision Model

In this paper, we present a collision model to stroboscopically simulate the dynamics of information in dissipative systems. In particular, an all-optical scheme is proposed to investigate the information scrambling of bosonic systems with Gaussian environmental states. Varying the states of environments, in the presence of dissipation, transient tripartite mutual information of system modes may show negative value, signaling the appearance of information scrambling. We also find that dynamical indivisibility based non-Markovianity plays dual roles in affecting the dynamics of information.     

The Influence of Non‐Markovian Characters on Quantum Adiabatic Evolution

The influence of non‐Markovian characters on the adiabatic evolution is investigated. The adiabatic Raman process is simulated in a three‐level system coupled to two independent environments. The results show that the memory effect of environments can restrain the decoherence effect of the system. Even if the system has strong decay rates in the non‐Markovian environments, the adiabatic population transfer can be still completed efficiently. Moreover, the memory effect can reduce the dependence of the adiabatic evolution on the Rabi frequency. Specifically, the two independent non‐Markovian baths can suppress the decoherence more effectively than a single non‐Markovian bath.     

Environment-Assisted Modulation of Heat Flux in a Bio-Inspired System Based on Collision Model

The high energy transfer efficiency of photosynthetic complexes has been a topic of research across many disciplines. Several attempts have been made in order to explain this energy transfer enhancement in terms of quantum mechanical resources such as energetic and vibration coherence and constructive effects of environmental noise. The developments in this line of research have inspired various biomimetic works aiming to use the underlying mechanisms in biological light harvesting complexes for the improvement of synthetic systems. In this article, we explore the effect of an auxiliary hierarchically structured environment interacting with a system on the steady-state heat transport across the system. The cold and hot baths are modeled by a series of identically prepared qubits in their respective thermal states, and we use a collision model to simulate the open quantum dynamics of the system. We investigate the effects of system-environment, inter-environment couplings and coherence of the structured environment on the steady state heat flux and find that such a coupling enhances the energy transfer. Our calculations reveal that there exists a non-monotonic and non-trivial relationship between the steady-state heat flux and the mentioned parameters.     

A Kinetic Model of Quantum Jumps

A new class of models describing the dissipative dynamics of an open quantum system S by means of random time evolutions of pure states in its Hilbert space is considered. The random evolutions are linear and defined by Poisson processes. At the random Poissonian times, the wavefunction experiences discontinuous changes (quantum jumps). These changes are implemented by some non-unitary linear operators satisfying a locality condition. If the Hilbert space of S is infinite dimensional, the models involve an infinite number of independent Poisson processes and the total frequency of jumps may be infinite. We show that the random evolutions in are then given by some almost-surely defined unbounded random evolution operators obtained by a limit procedure. The average evolution of the observables of S is given by a quantum dynamical semigroup, its generator having the Lindblad form.⁽¹⁾ The relevance of the models in the field of electronic transport in Anderson insulators is emphasised.     

Evaporative Cooling and Self‐Thermalization in an Open System of Interacting Fermions

Depletion dynamics of an open system of weakly interacting fermions with two‐body random interactions is studied. In this model, fermions are escaping from the high‐energy one‐particle orbitals, that mimics the evaporation process used in laboratory experiments with neutral atoms to cool them to ultra‐low temperatures. It is shown that due to self‐thermalization the system instantaneously adjusts to the new temperature which decreases with the course of time.     

Peculiarities of resonance fluorescence statistics for a two‐level atom in frequency selective feedback loop

A theoretical analysis of the resonance fluorescence of a two‐level atom in a classical monochromatic field with feedback phase switching depending on the fluorescence triplet component which the last spontaneously emitted photon belongs to is presented. The considered feedback loop is a hybrid quantum‐classical system. Statistics of photoemissions into the triplet components is investigated as well as correlations between the components. In contrast to the well‐known resonance fluorescence of a two‐level atom without feedback phase switching, a bunching of photocounts is predicted in each side‐band, and successive photoemissions into different side‐bands manifest antibunching. The type of the statistics can efficiently be controlled by the frequency detuning of the external field. In many points the considered feedback scheme provides drastically different statistical features of fluorescence when compared with the scheme of frequency‐unselective feedback phase switching.

     

Matrix Algebras in Non-Hermitian Quantum Mechanics

In principle, non-Hermitian quantum equations of motion can be formulated using as a starting point either the Heisenberg's or the Schrödinger's picture of quantum dynamics. Here it is shown in both cases how to map the algebra of commutators, defining the time evolution in terms of a non-Hermitian Hamiltonian, onto a non-Hamiltonian algebra with a Hermitian Hamiltonian. The logic behind such a derivation is reversible, so that any Hermitian Hamiltonian can be used in the formulation of non-Hermitian dynamics through a suitable algebra of generalized (non-Hamiltonian) commutators.
These results provide a general structure (a template) for non-Hermitian equations of motion to be used in the computer simulation of open quantum systems dynamics.     

One‐Step Implementation of N‐Qubit Nonadiabatic Holonomic Quantum Gates with Superconducting Qubits via Inverse Hamiltonian Engineering

A protocol is proposed to realize one‐step implementation of the N‐qubit nonadiabatic holonomic quantum gates with superconducting qubits. The inverse Hamiltonian engineering is applied in designing microwave pulses to drive superconducting qubits. By combining curve fitting, the wave shapes of the designed pulses can be described by simple functions, which are not hard to realize in experiments. To demonstrate the effectiveness of the protocol, a three‐qubit holonomic controlled π‐phase gate is taken as an example in numerical simulations. The results show that the protocol holds robustness against noise and decoherence. Therefore, the protocol may provide an alternative approach for implementing N‐qubit nonadiabatic holonomic quantum gates.     

Structural dynamics of 4‐cyanobenzaldehyde in S2(ππ*) state

The excited state structural dynamics of 4‐cyanobenzaldehyde (p‐CNB) were studied by using the resonance Raman spectroscopy and the quantum mechanical calculations. The experimental A‐ and B‐band absorptions were, respectively, assigned to the major n_O → π₃* and π₂ → π₃* transitions according to the B3LYP‐TD/6‐31G(d) and CIS/6‐31G(d) computations, and the resonance Raman spectra. It was determined that the actual S₂(π₂π₃) state was in energy lower than S₃(π₁π₃), which was just opposite to the B3LYP‐TD/6‐31G(d) calculated order of the S₂(π₁π₃) and S₃(π₂π₃). The vibrational assignments were carried out for the A‐ and B‐band resonance Raman spectra. The B‐band resonance Raman intensities of p‐CNB were dominated by the C2–C3/C5–C6 symmetric stretch mode ν₈, the overtones nν₈ and their combination bands with the ring C–H bend mode ν₁₇, the C9–N10 stretch mode ν₆, the C7–O8 stretch mode ν₇ and the remaining modes. The conical intersection between S₁(n_Oπ₃) and S₂(π₂π₃) states of p‐CNB was determined at complete active space self‐consistent field (CASSCF)(8,7)/6‐311G(d,p) level of theory. The B‐band short‐time structural dynamics and the corresponding decay dynamics of p‐CNB were obtained by analysis of the resonance Raman intensity pattern and CASSCF computations. The resonance Raman spectra indicated that CI[S₁(n_Oπ₃)/S₂(π₁π₂π₃π₄)] located nearby the Franck–Condon region. The excited state decay dynamics evolving from the S_{2, FC}(π₂π₃) to the S₁(n_Oπ₃) state was proposed. Copyright © 2013 John Wiley & Sons, Ltd.     

Quantum Darwinism in a Composite System: Objectivity versus Classicality

We investigate the implications of quantum Darwinism in a composite quantum system with interacting constituents exhibiting a decoherence-free subspace. We consider a two-qubit system coupled to an N-qubit environment via a dephasing interaction. For excitation preserving interactions between the system qubits, an analytical expression for the dynamics is obtained. It demonstrates that part of the system Hilbert space redundantly proliferates its information to the environment, while the remaining subspace is decoupled and preserves clear non-classical signatures. For measurements performed on the system, we establish that a non-zero quantum discord is shared between the composite system and the environment, thus violating the conditions of strong Darwinism. However, due to the asymmetry of quantum discord, the information shared with the environment is completely classical for measurements performed on the environment. Our results imply a dichotomy between objectivity and classicality that emerges when considering composite systems.     

Vibronic coupling and excited‐state reaction dynamics of pyrazine in 1 1B2u (1ππ*) state by resonance Raman spectroscopy and CASSCF calculation

The photophysics and photochemistry of pyrazine (C₄H₄N₂, D_2h) after excitation to the S₂ (1 ¹B_2u, ¹ππ*) electronic state were studied by using the resonance Raman spectroscopy and complete active space self‐consistent field method calculations. The B‐band resonance Raman spectra in cyclohexane solvent were obtained at 266.0, 252.7, and 245.9 nm excitation wavelengths to probe the structural dynamics of pyrazine in the S₂ (1 ¹B_2u, ¹ππ*) state. Three electronic states 1 ¹B_3u, 1 ¹B_1g, and 1 ¹B_2g were found to couple with the S₂ (1 ¹B_2u, ¹ππ*) state. Two conical intersection (CI) points CI[S₂(B_2u)/S₁(B_3u)] and CI[S₁/S₀] and one transition state of the isomerization between pyrazine and pyrimidine were predicted to play important roles in the photochemistry of pyrazine. On the basis of the calculations, the mechanism of the photoisomerization reaction between pyrazine and pyrimidine has been proposed. Copyright © 2012 John Wiley & Sons, Ltd.     

用Sin-DVR方法求解在绝热表象下锥形交叉分子振动本征态

在波恩-奥本海默近似中,分子中原子核的运动通常采用绝热表象的基态势能面来描述,一般情况下这样是比较好的近似. 然而当势能面上存在锥形交叉时,即使体系的能量远远低于锥形交叉点,绝热基态势能面近似将不再有效. 锥形交叉的出现,使得绝热表象下描述核运动的哈密顿中出现了两个额外的附加项：对角波恩－奥本海默近似校正(DBOC)项和几何相位(GP)项. 尤其GP项,使得基态绝热势能面近似失效. 这两项在锥形交叉点处的数值是发散的,因此在绝热表象中来严格描述核运动,会使量子动力学的计算存在数值收敛的困难. 在量子分子动力学计算中,最常用的数值方法是分离变量表象方法(DVR). 本文通过在绝热表象和透热表象下求解涉及两个电子态且包含锥形交叉的二维的薛定谔方程来验证Sinc-DVR的数值收敛性. 计算结果显示,在绝热表象中采用通常格点密度分布的Sinc-DVR方法,即使在没有特别的处理DBOC和GP项时,也可以得到比较可靠的结果. 此时的数值不确定性并没有比引入任意的向量势来纠正GP效应的不确定性更差. 需要特别注意的是,纠正GP效应的任意向量势的精确形式,通常是不易得到其精确形式的.     

Manifestation of conical intersections in resonance Raman intensities

This paper deals with the manifestations of conical intersections (CIs), unequivocal spectroscopic signatures of which are still elusive, in the resonance Raman intensities. In particular, the results of our calculations on the ‘two state‐two vibrational mode’ and the ‘two state‐three vibrational mode’ models are presented. The models comprise two excited states of different spatial symmetry, one bright and one dark, which are coupled by a nontotally symmetric mode while the energy gap between them is tuned by one/two totally symmetric modes. Time dependent theory for vibronically coupled states is employed for the calculation and analysis of Raman excitation profiles (REPs). The manifestation of intersections in REPs is studied by extensive model calculations and the results of two specific models are presented. The feasibility of using REPs to probe the role of CIs in polyatomic systems is ascertained by multimode calculations on two polyatomic systems viz., pyrazine and trans‐azobenzene. The study also notes the importance of the pump excitation wavelength dependence in a femtosecond time‐resolved experiment probing the intersection‐induced nonadiabatic dynamics. Copyright © 2009 John Wiley & Sons, Ltd.     

Stability of Optically Injected Two‐State Quantum‐Dot Lasers

Simultaneous two‐state lasing is a unique property of semiconductor quantum‐dot (QD) lasers. This not only changes steady‐state characteristics of the laser device but also its dynamic response to perturbations. In this paper we investigate the dynamic stability of QD lasers in an external optical injection setup. Compared to conventional single‐state laser devices, we find a strong suppression of dynamical instabilities in two‐state lasers. Furthermore, depending on the frequency and intensity of the injected light, pronounced areas of bistability between both lasing frequencies appear, which can be employed for fast optical switching in all‐optical photonic computing applications. These results emphasize the suitability of QD semiconductor lasers in future integrated optoelectronic systems where a high level of stability is required.