We study the generation of electronic ring currents in the presence of nonadiabatic coupling using circularly polarized light. For this, we introduce a solvable model consisting of an electron and a nucleus rotating around a common center and subject to their mutual Coulomb interaction. The simplicity of the model brings to the forefront the non-trivial properties of electronic ring currents in the presence of coupling to the nuclear coordinates and enables the characterization of various limiting situations transparently. Employing this model, we show that vibronic coupling effects play a crucial role even when a single E degenerate eigenstate of the system supports the current. The maximum current of a degenerate eigenstate depends on the strength of the nonadiabatic interactions. In the limit of large nuclear to electronic masses, in which the Born–Oppenheimer approximation becomes exact, constant ring currents and time-averaged oscillatory currents necessarily vanish.
The generation of electronic ring currents in ring-shaped molecules by photo-excitation with circularly polarized laser light is considered in the presence of vibronic coupling effects. (E × e) Jahn-Teller distortions, unavoidable by symmetry in the (E) subset of electronic states supporting the ring current, mix the clockwise and anti-clockwise circulation directions of the electrons and can suppress the maximum achievable current by at least one order of magnitude, already for moderate vibronic coupling strengths, as compared to the Born-Oppenheimer limit of fixed atomic positions. The circulation direction of the electrons is found to depend on the spectral region of the (E × e) Hamiltonian. This fact results in the surprising effect that the same polarization direction of the laser pulse can trigger either clockwise or anti-clockwise electronic dynamics depending on the wavelength of the photons. These findings are illustrated in a model of the triazine molecule.
Transition metal tetrahalides are a class of highly symmetric molecules for which very few spectroscopic data exist. Exploratory ab initio calculations of electronic potential energy functions indicate that the equilibrium molecular geometries of the vanadium, niobium, and tantalum tetrafluorides (i.e., VF4, NbF4, and TaF4) exhibit strong distortions from the tetrahedral configuration in their electronic ground state (2E) and first excited state (2T2) along the nuclear displacement coordinates of e symmetry. The distortions result from the E × e and T2 × e Jahn–Teller (JT) effects, respectively. In addition, there are weaker distortions in the 2T2 state along the coordinates of t2 symmetry due to the T2 × t2 JT effect. The description of the large-amplitude dynamics induced by these JT effects requires the construction of JT Hamiltonians beyond the standard model of JT theory, which is based on Taylor expansions up to second order in normal-mode displacements. These higher-order JT Hamiltonians were constructed in this work by expansions of the electronic potentials of the title molecule in terms of symmetry invariant polynomials in symmetry-adapted nuclear displacement coordinates for the bending modes of VF4. A multi-configuration electronic structure method was employed to determine the coefficients of these high-order polynomial expansions from first principles. Using these large-amplitude Jahn–Teller Hamiltonians, the vibronic spectra of VF4 were computed. The spectra illustrate the effects of large-amplitude fluxional nonadiabatic dynamics due to exceptionally strong E × e and T2 × e JT couplings. In addition, the vibronic spectrum of the T2 × (e + t2) JT effect, including the bending mode of t2 symmetry, was computed. The spectrum displays strong inter-mode coupling effects exhibiting a vibronic structure, which is substantially different from that predicted by independent-mode approximation. These results represent the first ab initio study of dynamical Jahn–Teller effects in VF4.
A first principles quantum dynamics study of N-H photodissociation of pyrrole on the S-πσ(A21) coupled electronic states is carried out with the aid of an optimally designed UV-laser pulse. A new photodissociation path, as compared to the conventional barrier crossing on the πσ*1 state, opens up upon electronic transitions under the influence of pump-dump laser pulses, which efficiently populate both the dissociation channels. The interplay of electronic transitions due both to vibronic coupling and the laser pulse is observed in the control mechanism and discussed in detail. The proposed control mechanism seems to be robust, and not discussed in the literature so far, and is expected to trigger future experiments on the πσ*1 photochemistry of molecules of chemical and biological importance. The design of the optimal pulses and their application to enhance the overall dissociation probability is carried out within the framework of optimal control theory. The quantum dynamics of the system in the presence of pulse is treated by solving the time-dependent Schrödinger equation in the semi-classical dipole approximation.
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