Quantum Mechanical Investigation of Mode-Specific Tunneling upon Fundamental Excitation in Malonaldehyde

We present a quantum mechanical study of mode-specific tunneling upon fundamental excitation in malonaldehyde with a multidimensional theory that utilizes the saddle-point normal coordinates. We find that a ring-deformation normal mode is as essential as the well-known imaginary-frequency normal mode in the multidimensional investigation. The changes in tunneling splittings upon fundamental excitation are calculated. The results are competitive with those from a recently developed mixed classical-quantum method. Moreover, the results are qualitatively consistent with experiment for about half of all the modes.