TY - JOUR
T1 - Small Matrix Quantum-Classical Path Integral
AU - Kundu, Sohang
AU - Makri, Nancy
N1 - Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
PY - 2022/4/21
Y1 - 2022/4/21
N2 - The quantum-classical path integral (QCPI) is a rigorous formulation of nonadiabatic dynamics, where the dynamical interaction between a quantum system and its environment is captured consistently through classical trajectories driven by forces along quantum paths of the system. In this Letter, we develop a small matrix decomposition (SMatQCPI) that eliminates the tensor storage requirements of the iterative QCPI algorithm. In the case of a system coupled to a harmonic bath, SMatQCPI provides fully quantum mechanical propagation, which also reduces the computational cost to that of a single QCPI step. Further, the SMatQCPI matrices only need to account for quantum contributions to decoherence, allowing high efficiency in challenging regimes of incoherent dynamics. Overall, this new composite algorithm combines the best features of two powerful path integral formulations and offers a versatile tool for simulating condensed phase quantum dynamics.
AB - The quantum-classical path integral (QCPI) is a rigorous formulation of nonadiabatic dynamics, where the dynamical interaction between a quantum system and its environment is captured consistently through classical trajectories driven by forces along quantum paths of the system. In this Letter, we develop a small matrix decomposition (SMatQCPI) that eliminates the tensor storage requirements of the iterative QCPI algorithm. In the case of a system coupled to a harmonic bath, SMatQCPI provides fully quantum mechanical propagation, which also reduces the computational cost to that of a single QCPI step. Further, the SMatQCPI matrices only need to account for quantum contributions to decoherence, allowing high efficiency in challenging regimes of incoherent dynamics. Overall, this new composite algorithm combines the best features of two powerful path integral formulations and offers a versatile tool for simulating condensed phase quantum dynamics.
UR - http://www.scopus.com/inward/record.url?scp=85128796106&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85128796106&partnerID=8YFLogxK
U2 - 10.1021/acs.jpclett.2c00668
DO - 10.1021/acs.jpclett.2c00668
M3 - Article
C2 - 35416671
AN - SCOPUS:85128796106
SN - 1948-7185
VL - 13
SP - 3492
EP - 3498
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 15
ER -