Quantum dynamics and spectroscopy of dihalogens in solid matrices. I. Efficient simulation of the photodynamics of the embedded ${\mathrm{I}}_2\mathrm{K}{\mathrm{r}}_{18}$ cluster using the G-MCTDH method

Abstract

The molecular dynamics following the electronic $B{}^3{\Pi }_u\left(0^{+}\right)⟵X{}^1{\Sigma }_g^{+}$ photoexcitation of the iodine molecule embedded in solid krypton are studied quantum mechanically using the Gaussian variant of the multiconfigurational time-dependent Hartree method (G-MCTDH). The accuracy of the Gaussian wave packet approximation is validated against numerically exact MCTDH simulations for a fully anharmonic seven-dimensional model of the ${\mathrm{I}}_2\mathrm{K}{\mathrm{r}}_{18}$ cluster in a crystal Kr cage. The linear absorption spectrum, time-evolving vibrational probability densities, and ${\mathrm{I}}_2$ energy expectation value are accurately reproduced by the numerically efficient G-MCTDH approach. The reduced density matrix of the chromophore is analyzed in the coordinate, Wigner and energy representations, so as to obtain a multifaceted dynamical view of the guest-host interactions. Vibrational coherences extending over the bond distance range $ 2.7\,\mboxÅ < R_\mathrm{I-I} < 4.0\,\mboxÅ$ are found to survive for several vibrational periods, despite extensive dissipation. The present results prepare the ground for the simulation of time-resolved coherent Raman spectroscopy of the ${\mathrm{I}}_2$-krypton system addressed in a companion paper.

References in corpus (7)

• Long-lived quantum coherence in photosynthetic complexes at physiological temperature
• Negativity of the Wigner function as an indicator of nonclassicality
• Nonlinear optical signals and spectroscopy with quantum light
• Vibronic phenomena and exciton-vibrational interference in two-dimensional spectra of molecular aggregates
• Wigner functions, squeezing properties and slow decoherence of atomic Schrodinger cats
• Vibrational spectroscopy via the Caldeira-Leggett model with anharmonic system potentials
• 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

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• Semiclassical vibrational spectroscopy with Hessian databases
• 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
• Time evolution as an optimization problem: The hydrogen atom in strong laser fields in a basis of time-dependent Gaussian wave packets