Improved semiclassical dynamics through adiabatic switching trajectory sampling

Abstract

We introduce an improved semiclassical dynamics approach to quantum vibrational spectroscopy. In this method, a harmonic-based phase space sampling is preliminarily driven toward non-harmonic quantization by slowly switching on the actual potential. The new coordinates and momenta serve as initial conditions for the semiclassical dynamics calculation, leading to a substantial decrease in the number of chaotic trajectories to deal with. Applications are presented for model and molecular systems of increasing dimensionality characterized by moderate or high chaoticity. They include a bidimensional Henon-Heiles potential, water, formaldehyde, and methane.The method improves accuracy and precision of semiclassical results and it can be easily interfaced with all pre-existing semiclassical theories.

References in corpus (22)

• First-Principles Semiclassical Initial Value Representation Molecular Dynamics
• Semiclassical "Divide-and-Conquer" Method for Spectroscopic Calculations of High Dimensional Molecular Systems
• On-the-fly ab initio semiclassical dynamics: Identifying degrees of freedom essential for emission spectra of oligothiophenes
• On-the-fly ab initio semiclassical evaluation of absorption spectra of polyatomic molecules beyond the Condon approximation
• Single-Hessian thawed Gaussian approximation: The missing rung on the ladder
• 'Divide-and-conquer' semiclassical molecular dynamics: An application to water clusters
• Nonadiabatic semiclassical dynamics in the mixed quantum-classical initial value representation
• The Importance of the Pre-exponential Factor in Semiclassical Molecular Dynamics
• "Divide and Conquer" Semiclassical Molecular Dynamics: A practical method for Spectroscopic calculations of High Dimensional Molecular Systems
• Mixed Semiclassical Initial Value Representation Time-Averaging Propagator for Spectroscopic Calculations
• Anharmonic Vibrational Eigenfunctions and Infrared Spectra from Semiclassical Molecular Dynamics
• Simplified Approach to the Mixed Time-averaging Semiclassical Initial Value Representation for the Calculation of Dense Vibrational Spectra
• Herman-Kluk propagator is free from zero-point energy leakage
• An Effective Semiclassical Approach to IR Spectroscopy
• Validating and Implementing Modified Filinov Phase Filtration in Semiclassical Dynamics
• Graphics processing units accelerated semiclassical initial value representation molecular dynamics
• Application of the Mixed Time-averaging Semiclassical Initial Value Representation method to Complex Molecular Spectra
• Reduced Rovibrational Coupling Cartesian Dynamics for Semiclassical Calculations: Application to the Spectrum of the Zundel Cation
• Vibrational Investigation of Nucleobases by Means of Divide and Conquer Semiclassical Dynamics
• Semiclassical vibrational spectroscopy with Hessian databases
• A quantum mechanical insight into SN2 reactions: Semiclassical initial value representation calculations of vibrational features of the Cl${}^{-}$--CH${}_3$Cl pre-reaction complex with the VENUS suite of codes
• Semiclassical dynamics in the mixed quantum-classical limit

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