Chatterjee Sambarta, Makri Nancy
Department of Chemistry, University of Illinois, Urbana, IL 61801, USA.
Phys Chem Chem Phys. 2021 Mar 11;23(9):5125-5133. doi: 10.1039/d0cp05528j.
We investigate the time evolution of the reduced density matrix (RDM) and its purity in the dynamics of a two-level system coupled to a dissipative harmonic bath, when the system is initially placed in one of its eigenstates. We point out that the symmetry of the initial condition confines the motion of the RDM elements to a one-dimensional subspace and show that the purity always goes through its maximally mixed value at some time during relaxation, but subsequently recovers and (under low-temperature, weakly dissipative conditions) can rise to values that approach unity. These behaviors are quantified through accurate path integral calculations. Under low-temperature, weakly dissipative conditions, we observe unusual, nonmonotonic population dynamics when the two-level system is initially placed in its ground state. We also analyze the origin of the system-bath interactions responsible for the nonmonotonic behavior of purity during relaxation. Our results show that classical dephasing processes arising from site level fluctuations lead to a monotonic decay of purity, and that the quantum mechanical decoherence events associated with spontaneous phonon emission are responsible for the subsequent recovery of purity. Last, we show that coupling with a low-temperature bath can purify a mixed two-level system. In the case of the maximally mixed initial RDM, the purity increases monotonically even during short time.
我们研究了一个与耗散性谐振子浴耦合的二能级系统动力学中约化密度矩阵(RDM)及其纯度的时间演化,此时系统初始处于其本征态之一。我们指出初始条件的对称性将RDM元素的运动限制在一个一维子空间,并表明纯度在弛豫过程中的某个时刻总会经过其最大混合值,但随后会恢复,并且(在低温、弱耗散条件下)可以上升到接近1的值。这些行为通过精确的路径积分计算进行量化。在低温、弱耗散条件下,当二能级系统初始处于基态时,我们观察到异常的、非单调的布居动力学。我们还分析了在弛豫过程中导致纯度非单调行为的系统 - 浴相互作用的起源。我们的结果表明,由位点能级涨落引起的经典退相过程导致纯度单调衰减,而与自发声子发射相关的量子力学退相干事件是纯度随后恢复的原因。最后,我们表明与低温浴耦合可以纯化一个混合的二能级系统。在初始RDM最大混合的情况下,即使在短时间内纯度也会单调增加。