Medeiros Harder (throatlist80)

[n]Cycloparaphenylene ([n]CPP) molecules have attracted broad interests due to their unique properties resulting from the distorted and strained aromatic hoop structures. In this work, we apply sub-nanometer resolved tip-enhanced Raman spectroscopy (TERS) to investigate the adsorption configurations and structural deformations of [12]CPP molecules on metal substrates with different crystallographic orientations. The TERS spectra for a [12]CPP molecule adsorbed on the isotropic Cu(100) surface are found to be essentially the same over the whole nanohoop, indicating an alternately twisted structure that is similar to the [12]CPP molecule in free space. However, when the [12]CPP molecules are adsorbed on the anisotropic Ag(110) surface, the molecular shape is found to be severely deformed into two types of adsorption configurations one showing an interesting "Möbius-like" feature and the other showing a symmetric bending structure. Their TERS spectral features are found to be site-dependent over the hoop and even show peak splitting for the out-of-plane C-H bending vibrations. The deformed structural models gain strong support from the spatial distribution of "symmetric" TERS spectra at different positions on the hoop. Further TERS imaging, with a spatial resolution down to ∼2 Å, provides a panoramic view on the local structural deformations caused by different tilting of the benzene units in real space, which offers insights into the subtle changes in the aromatic properties over the deformed hoop owing to inhomogeneous molecule-substrate interactions. The ability of TERS to probe the molecular structure and local deformation at the sub-molecular level, as demonstrated here, is important for understanding surface science as well as molecular electronics and optoelectronics at the nanoscale.Understanding and managing the influence that either external forces or non-equilibrated environments may have on chemical processes is essential for the current and future development of theoretical chemistry. One of the central questions to solve is how to generalize the transition state theory in order to make it applicable in far from equilibrium situations. In this sense, here we propose a way to generalize Eyring's equation based on the definition of an effective thermal energy (temperature) emerging from the coupling of both fast and slow dynamic variables analyzed within the generalized Langevin dynamics scheme. This coupling makes the energy distribution of the fast degrees of freedom not equilibrate because they have been enslaved to the dynamics of the corresponding slow degrees. However, the introduction of the effective thermal energy enables us to restore an effective adiabatic separation of timescales leading to a renormalization of the generalized fluctuation-dissipation theorem. Hence, this procedure opens the possibility to deal with systems far away from equilibrium. A significant consequence of our results is that Eyring's equation is generalized to treat systems under the influence of strong external forces.The tailored coupled cluster (TCC) approach is a promising ansatz that preserves the simplicity of single-reference coupled cluster theory while incorporating a multi-reference wave function through amplitudes obtained from a preceding multi-configurational calculation. Here, we present a detailed analysis of the TCC wave function based on model systems, which require an accurate description of both static and dynamic correlation. We investigate the reliability of the TCC approach with respect to the exact wave function. In addition to the error in the electronic energy and standard coupled cluster diagnostics, we exploit the overlap of TCC and full configuration interaction wave functions as a quality measure. We critically review issues, such as the required size of the active space, size-consistency, symmetry breaking in the wave function, and the dependence of TCC on the reference wave function. We observe that po