Using Diffusion Monte Carlo Wave Functions to Analyze the Vibrational Spectra of HO and HO.

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.

Spectral signatures of proton delocalization in H(HO) ions.

Couplings involving large amplitude vibrations in H+(H2O)n (n = 1-4) are explored using several theoretical approaches. These include harmonic treatments, analysis of harmonically coupled anharmonic oscillator (HCAO) models of the OH stretching vibrations, vibrational perturbation theory (VPT2) in internal coordinates, and diffusion Monte Carlo (DMC). It is found that couplings between shared proton stretches and HOH bends can lead to normal modes that are significantly mixed in character.

Role of Torsion-Vibration Coupling in the Overtone Spectrum and Vibrationally Mediated Photochemistry of CHOOH and HOOH.

The yield of vibrationally excited OH fragments resulting from the vibrationally mediated photodissociation of methyl hydroperoxide (CHOOH) excited in the vicinity of its 2ν and 3ν stretching overtones is compared with that resulting from excitation of the molecule to states with three quanta in the CH stretches and to the state with two quanta in the OH stretch and one in the OOH bend (2ν + ν). We find that the OH fragment vibrational state distribution depends strongly on the vibrational state of CHOOH prior to photodissociation. Specifically, dissociation from the CH stretch overtones and the stretch/bend combination band involving the OH stretch and OOH bend produced significantly less vibrationally excited OH fragments compared to that produced following excitation of CHOOH to an overtone in the OH stretch.

Spectroscopic snapshots of the proton-transfer mechanism in water.

The Grotthuss mechanism explains the anomalously high proton mobility in water as a sequence of proton transfers along a hydrogen-bonded (H-bonded) network. However, the vibrational spectroscopic signatures of this process are masked by the diffuse nature of the key bands in bulk water. Here we report how the much simpler vibrational spectra of cold, composition-selected heavy water clusters, D(DO), can be exploited to capture clear markers that encode the collective reaction coordinate along the proton-transfer event.

Microhydration of contact ion pairs in M(2+)OH(-)(H2O)(n=1-5) (M = Mg, Ca) clusters: spectral manifestations of a mobile proton defect in the first hydration shell.

Vibrational predissociation spectra of D2-"tagged" Mg(2+)OH(-)(H2O)n=1-6 and Ca(2+)OH(-)(H2O)n=1-5 clusters are reported to explore how the M(2+)OH(-) contact ion pairs respond to stepwise formation of the first hydration shell. In both cases, the hydroxide stretching frequency is found to red-shift strongly starting with addition of the third water molecule, quickly becoming indistinguishable from nonbonded OH groups associated with solvent water molecules by n = 5. A remarkably broad feature centered around 3200 cm(-1) and spanning up to ∼1000 cm(-1) appears for the n ≥ 4 clusters that we assign to a single-donor ionic hydrogen bond between a proximal first solvent shell water molecule and the embedded hydroxide ion.