Coherent state based solutions of the time-dependent Schrödinger equation: hierarchy of approximations to the variational principle. Issue 1 (2nd January 2021)

• Record Type: Journal Article
• Authors: Werther, Michael; Choudhury, Sreeja Loho; Großmann, Frank
• Is Part Of: International reviews in physical chemistry. Volume 40:Issue 1(2021)
• Page Start: 81
• Page End: 125
• Publication Date: 2021-01-02
• Subjects: Coherent states -- Schrödinger equation -- variational principle -- Morse oscillator; Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1080/0144235X.2020.1823168
• Languages: English
• ISSNs: 0144-235X

Abstract

Abstract : In this review, we give a comprehensive comparison of the most widely used coherent state (CS) based methods to solve the time-dependent Schrödinger equation (TDSE). Starting from the fully variational coherent states (VCS) method, after a first approximation, the coupled coherent states (CCS) method can be derived, whereas an additional approximation leads to the semiclassical Herman–Kluk (HK) method. We numerically compare the different methods with another one, based on a static rectangular grid of coherent states (SCS), by applying all of them to the revival dynamics in a 1D Morse oscillator, with a special focus on the number of basis states (for the CCS and HK methods the number of classical trajectories) needed for convergence and the related issue of tight frames, which in principle allow the usage of CSs as if they were orthogonal. Different discretisation strategies for the occurring phase space integrals for systems with more degrees of freedom are also discussed and the apoptosis procedure that allows to circumvent the linear dependency problem in the VCS method is reviewed. The Holstein molecular crystal model serves to further illustrate the latter point.