Simplified Approach to the Mixed Time-averaging Semiclassical Initial Value Representation for the Calculation of Dense Vibrational Spectra

Abstract

We present and test an approximate method for the semiclassical calculation of vibrational spectra. The approach is based on the mixed time-averaging semiclassical initial value representation method, which is simplified to a form that contains a filter to remove contributions from approximately harmonic environmental degrees of freedom. This filter comes at no additional numerical cost, and it has no negative effect on the accuracy of peaks from the anharmonic system of interest. The method is successfully tested for a model Hamiltonian, and then applied to the study of the frequency shift of iodine in a krypton matrix. Using a hierarchic model with up to 108 normal modes included in the calculation, we show how the dynamical interaction between iodine and krypton yields results for the lowest excited iodine peaks that reproduce experimental findings to a high degree of accuracy.

References in corpus (12)

• How to remove the spurious resonances from ring polymer molecular dynamics
• Mapping Variable Ring Polymer Molecular Dynamics: A Path-Integral Based Method for Nonadiabatic Processes
• Direct simulation of electron transfer using ring polymer molecular dynamics: Comparison with semiclassical instanton theory and exact quantum methods
• 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
• 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
• 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
• Quantum initial condition sampling for linearized density matrix dynamics: Vibrational pure dephasing of iodine in krypton matrices

Cited by in corpus (17)

• On-the-fly ab initio semiclassical evaluation of vibronic spectra at finite temperature
• Anharmonic Vibrational Eigenfunctions and Infrared Spectra from Semiclassical Molecular Dynamics
• Deep zoom-in simulation of a fuzzy dark matter galactic halo
• On-the-fly ab initio semiclassical evaluation of time-resolved electronic spectra
• An Effective Semiclassical Approach to IR Spectroscopy
• Herman-Kluk propagator is free from zero-point energy leakage
• Improved semiclassical dynamics through adiabatic switching trajectory sampling
• 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
• On-the-fly ab initio three thawed Gaussians approximation: A semiclassical approach to Herzberg-Teller spectra
• Semiclassical vibrational spectroscopy with Hessian databases
• Representing Molecular Ground and Excited Vibrational Eigenstates with Nuclear Densities obtained from Semiclassical Initial Value Representation Molecular Dynamics
• A Semiclassical Framework for Mixed Quantum Classical Dynamics
• Semiclassical dynamics in the mixed quantum-classical limit
• Quantum dynamics and spectroscopy of dihalogens in solid matrices. II. Theoretical aspects and G-MCTDH simulations of time-resolved coherent Raman spectra of Schrödinger cat states of the embedded ${\mathrm{I}}_2\mathrm{K}{\mathrm{r}}_{18}$ cluster
• Sampling strategies for the Herman-Kluk propagator of the wavefunction
• Refined approach to cellularization: going from Heller's thawed Gaussian approximation to the Herman--Kluk propagator