The ground state tunneling splitting of malonaldehyde: Accurate full dimensional quantum dynamics calculations
Résumé
Benchmark calculations of the tunneling splitting in malonaldehyde using the full dimensional potential proposed by Yagi et al. [J. Chem. Phys. 115, 10647 (2001)] are reported. Two exact quantum dynamics methods are used: the multiconfigurational time-dependent Hartree (MCTDH) approach and the diffusion Monte Carlo based projection operator imaginary time spectral evolution (POITSE) method. A ground state tunneling splitting of 25.7±0.3 cm−125.7±0.3 cm−1 is calculated using POITSE. The MCTDH computation yields 25 cm−125 cm−1 converged to about 10% accuracy. These rigorous results are used to evaluate the accuracy of approximate dynamical approaches, e.g., the instanton theory.
Origine : Fichiers éditeurs autorisés sur une archive ouverte
Loading...