Using Diffusion Monte Carlo Wave Functions to Analyze the Vibrational Spectra of H7O3+ and H9O4+

An approach for evaluating spectra from ground state probability amplitudes (GSPA) obtained from diffusion Monte Carlo (DMC) simulations is extended to improve the description of excited state energies and allow for coupling among vibrational excited states. This approach is applied to studies of the protonated water trimer and tetramer, and their deuterated analogs. These ions provide models for solvated hydronium, and analysis of these spectra provides insights into spectral signatures of proton transfer in aqueous environments. In this approach, we obtain a separable set of internal coordinates from the DMC ground state probability amplitude. A basis is then developed from products of the DMC ground state wave function and low-order polynomials in these internal coordinates. This approach provides a compact basis in which the Hamiltonian and dipole moment matrix are evaluated and used to obtain the spectrum. The resulting spectra are in good agreement with experiment and in many cases provide comparable agreement to the results obtained using much larger basis sets. In addition, the compact basis allows for interpretation of the spectral features and how they evolve with cluster size and deuteration.

Automated summary

An approach for evaluating spectra from GSPA obtained from DMC simulations is extended to improve the description of excited state energies and allow for coupling among vibrational excited states. By extracting internal coordinates from the DMC ground state probability amplitude and developing a compact basis, the method provides good agreement with experimental results, allowing for interpretation of spectral features and their evolution with cluster size and deuteration.