Centroid molecular dynamics (CMD) and ring polymer molecular dynamics (RPMD) are two conceptually distinct extensions of path integral molecular dynamics that are able to generate approximate quantum dynamics of complex molecular systems. Both methods can be used to compute quasiclassical time correlation functions which have direct application in molecular spectroscopy; in particular, to infrared spectroscopy via dipole autocorrelation functions. The performance of both methods for computing vibrational spectra of several simple but representative molecular model systems is investigated systematically as a function of temperature and isotopic substitution. In this context both CMD and RPMD feature intrinsic problems which are quantified and investigated in detail. Based on the obtained results guidelines for using CMD and RPMD to compute infrared spectra of molecular systems are provided.

For decades, protonated methane, CH(5)(+), has provided new surprises and challenges for both experimentalists and theoreticians. This is because of the correlated large-amplitude motion of its five protons around the carbon nucleus, which leads to so-called hydrogen scrambling and causes a fluxional molecular structure. Here, the infrared spectra of all its H/D isotopologues have been measured using the 'Laser Induced Reactions' technique. Their shapes are found to be extremely dissimilar and depend strongly on the level of deuteration (only CD(5)(+) is similar to CH(5)(+)). All the spectra can be reproduced and assigned based on ab initio quantum simulations. The occupation of the topologically different sites by protons and deuterons is found to be strongly non-combinatorial and thus non-classical. This purely quantum-statistical effect implies a breaking of the classical symmetry of the site occupations induced by zero-point fluctuations, and this phenomenon is key to understanding the spectral changes studied here.

Spin-crossover metal complexes are highly promising magnetic molecular switches for prospective molecule-based devices. The spin-crossover molecular photoswitches developed so far operate either at very low temperatures or in the liquid phase, which hinders practical applications. Herein, we present a molecular spin-crossover iron(II) complex that can be switched between paramagnetic high-spin and diamagnetic low-spin states with light at room temperature in the solid state. The reversible photoswitching is induced by alternating irradiation with ultraviolet and visible light and proceeds at the molecular level.

The valence-tautomeric six-coordinate complex [Co(tbdiox)2(4-papy)2] (1; tbdiox = redox-active 3,5-di-tert-butyl-o-dioxolene, 4-papy = 4-phenylazopyridine) was synthesized and its electronic structure examined. Whereas 1 shows regular thermally driven valence tautomerism in the solid state, it partially dissociates in solution to form the five-coordinate species [Co(tbdiox)2(4-papy)] (2) and free 4-papy. Species 1 and 2 exhibit different electronic structures-low-spin (ls) Co(III) and high-spin (hs) Co(II), respectively-in solution at room temperature and therefore different magnetic properties. Since 1 and 2 are in an equilibrium that is 4-papy-dependent, the magnetic moment of the solution species can be tuned by means of the ligand content. Thus, the concept of coordination-induced valence tautomerism (CIVT) has been introduced. The electronic structures of 1 and 2 as well as their CIVT were elucidated by X-ray crystallography, electrochemistry, titration experiments, and all variable-temperature SQUID susceptometry, NMR, EPR, and electronic absorption spectroscopy. The experimental findings are strongly supported by broken-symmetry DFT calculations. The magnetic exchange interactions in different types of valence-tautomeric cobalt complexes were explored computationally.

Centroid molecular dynamics (CMD) is a popular method to extract approximate quantum dynamics from path integral simulations. Very recently we have shown that CMD gas phase infrared spectra exhibit significant artificial redshifts of stretching peaks, due to the so-called "curvature problem" imprinted by the effective centroid potential. Here we provide evidence that for condensed phases, and in particular for liquid water, CMD produces pronounced artificial redshifts for high-frequency vibrations such as the OH stretching band. This peculiar behavior intrinsic to the CMD method explains part of the unexpectedly large quantum redshifts of the stretching band of liquid water compared to classical frequencies, which is improved after applying a simple and rough "harmonic curvature correction."

The structure and electronic interface properties of five differently substituted benzenethiol based self-assembled monolayers (SAMs) on Cu(100) have been studied by means of low energy electron diffraction, thermal desorption spectroscopy, X-ray absorption spectroscopy (NEXAFS), and UV photoelectron spectroscopy. Because highly ordered SAMs are formed of which lateral density had been precisely determined, effective molecular dipole moments were derived from the measured work function shifts. These values are compared with gas phase dipole moments computed by quantum chemical calculations for the individual thiol molecules considering the molecular orientation determined from NEXAFS data. Furthermore, this comparison yields clear evidence for a coverage dependent depolarization effect of the adsorbed molecules within the SAMs.

Oxygen vacancies on ZnO(0001) have been proposed to be the catalytically active sites for methanol synthesis on pure ZnO. The charge state and thus the chemical reactivity of such vacancies on this polar O-terminated basal plane of ZnO is expected to be intimately connected to the degree of its hydroxylation in view of its Tasker type(3) unstable character. Here, the interplay between hydrogen adsorption and the thermodynamic stability of O vacancies in various charge states, corresponding formally to F(++), F(+), F(0), F(-), and F(--) centers, is investigated using electronic structure calculations. Assuming thermodynamic equilibrium of the defective surface with a hydrogen containing gas phase the thermodynamically most stable O vacancy type is determined as a function of temperature and pressure. For the adsorption of H(2) molecules at O vacancy sites it is found that the homolytic process leads to energetically more favorable structures than heterolytic adsorption and hydride formation. By homolytic adsorption and desorption one can switch between F(++), F(0), and F(--) or between F(+) and F(-), a process which is believed to occur during methanol synthesis. However, the barrier for heterolytic dissociation of H(2) at O vacancies is significantly lower compared to homolytic cleavage. Furthermore, the barrier for transforming hydridic hydrogen, i.e., ZnH species, to protonic hydrogen, i.e., OH species together with a reduction of ZnO itself, is quite high. This implies that hydridic H(-) species created as a result of heterolytic dissociation might have a long enough lifetime at O vacancies that they will be available for methanol synthesis. ZnH and OH vibrational frequencies have been computed in order to assist future experimental assignments.

A unique molecular switch – a cobalt dioxolene complex featuring photoisomerizable ligands – allows unprecedented control of magnetic properties with light at room temperature.