The ground state tunneling splitting of malonaldehyde: Accurate full dimensional quantum dynamics calculations

Benchmark calculations of the tunneling splitting in malonaldehyde using the full dimensional potential proposed by Yagi [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(-1) is calculated using POITSE. The MCTDH computation yields 25 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. (C) 2004 American Institute of Physics. (C) 2004 American Institute of Physics.