Multisurface Multimode Molecular Dynamical Simulation of Naphthalene and Anthracene Radical Cations by Using Nearly Linear Scalable Time-Dependent Discrete Variable Representation Method

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 118; no. 49; pp. 11451 - 11470
• Main Authors: Khan, Basir Ahamed, Sardar, Subhankar, Sarkar, Pranab, Adhikari, Satrajit
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 11.12.2014
• Subjects: Algorithms; Computation; Computer simulation; Dynamical systems; Dynamics; Mathematical models; Parallel processing; Spectra
• ISSN: 1089-5639; 1520-5215; 1520-5215
• DOI: 10.1021/jp507459m

The major portion of the algorithm of the time-dependent discrete variable representation (TDDVR) method is recently parallelized using the shared-memory parallelization scheme with the aim of performing dynamics on relatively large molecular systems. Because of the astronomical importance of naphthalene and anthracene, we have investigated their radical cations as models for theoretical simulation of complex photoelectron spectra and nonradiative decay process using the newly implemented parallel TDDVR code. The strong vibronic coupling among the six lowest doublet electronic states makes these polynuclear hydrocarbons dynamically important. The aim of the present investigation is to show the efficiency of our current TDDVR algorithm to perform dynamics on large dimensional quantum systems in vibronically coupled electronic manifold. Both the sequential and the parallelized TDDVR algorithms are almost linear scalable for an increase in number of processors. Because a significant speed-up is achieved by cycling in the correct way over arrays, all of the simulations are performed within a reasonable wall clock time. Our theoretical spectra well reproduce the features of the corresponding experimental analog. The dynamical outcomes, for example, population, photoelectron spectra, and diffused interstellar bands, etc., of our quantum-classical approach show good agreement with the findings of the well-established quantum dynamical method, that is, multi configuration time-dependent Hartree (MCTDH) approach.