Excited-state trajectories computed at the complete active space second-order perturbation theory (CASPT2) reveal how vibrational excitation controls the molecular approach to the intersection space that drives the photodissociation of a prototypical halogenated methyl radical, namely CF2I. Translating the Franck-Condon structure along the ground-state CASPT2 vibrational modes in this system fo...

The laser induced fluoresence excitation spectrum for the à A1 ↔ X̃ 2E transition of the methoxy radical has been reinvestigated. An extensive set of vibrational levels has been assigned with the aid of increased vibrational and rotational cooling. Many of these vibrational assignments are confirmed by rotational analysis of bands involving both the symmetric and asymmetric fundamentals of the Ã...

The theory of pump–probe diffraction experiments shows that probability density distributions of vibrational wave functions are experimentally observable. In the experiment a laser prepares a molecule in a selected vibrational state, in either the same or a different electronic manifold. The diffraction pattern of the molecule in the excited state is the Fourier transform image of the nuclear p...

Quantum state-resolved reactivity measurements probe the role of vibrational symmetry on the vibrational activation of the dissociative chemisorption of CH4 on Pt(111). IR-IR double resonance excitation in a molecular beam is used to prepare CH4 in all three different vibrational symmetry components A1, E, and F2 of the 2ν3 antisymmetric stretch overtone vibration. Methyl dissociation products ...

Nonlinear vibrational spectroscopy provides insights into the dynamics of vibrational energy transfer in and between molecules, a crucial phenomenon in condensed phase physics, chemistry, and biology. Here we use frequency-domain 2-dimensional infrared (2DIR) spectroscopy to investigate the vibrational relaxation (VR) and vibrational energy transfer (VET) rates in different solvents in both the...

Ultrafast transient electronic absorption, one- and two- dimensional electronic-vibrational spectroscopies were used to study the nonradiative relaxation dynamics of β-apo-8'-carotenal (bapo), a model aldehyde containing carotenoid, in cyclohexane and acetonitrile solutions. 2D electronic-vibrational (2DEV) spectroscopy allows for a direct correlation between the intrinsically coupled electroni...

We study the entanglement between the 2D vibrational motion and two ground state hyperfine levels of a trapped ion, Under particular conditions this entanglement depends on the parity of the total initial vibrational quanta. We study the robustness of this quantum coherence effect with respect to the presence of non-dissipative sources of decoherence, and of an imperfect initial state preparation.

Linear response functions are implemented for a vibrational configuration interaction state allowing accurate analytical calculations of pure vibrational contributions to dynamical polarizabilities. Sample calculations are presented for the pure vibrational contributions to the polarizabilities of water and formaldehyde. We discuss the convergence of the results with respect to various details ...

This paper discusses the feasibility of high-frequency nonlinear vibrational control. Such control has the advantage that it does not require state measurement and processing capabilities that are required in conventional feedback control. Bellman et al. [1] investigated nonlinear systems controlled by linear vibrational controllers and proved that vibrational control is not feasible if the Jac...