Excitation of degenerate vibrations in non-degenerate electronic bands

The vibrational rule structuic of the 2A'₁ band in the photoelectron spectrum of BF₃ is analyzed Using ab initio calculated coupling constants, It is shown that some lines of this spectrum represent excitation of single quanta of the degenerate stretching vibration They borrow their intensity from the adjacent 2E' state via a pseudo-Jahn-Teller interaction     

Barrierless Single‐Electron‐Induced cis–trans Isomerization

Lowering the activation energy of a chemical reaction is an essential part in controlling chemical reactions. By attaching a single electron, a barrierless path for the cis–trans isomerization of maleonitrile on the anionic surface is formed. The anionic activation can be applied in both reaction directions, yielding the desired isomer. We identify the microscopic mechanism that leads to the formation of the barrierless route for the electron‐induced isomerization. The generalization to other chemical reactions is discussed.     

Combined experimental-theoretical study of the lower excited singlet states of paravinyl phenol, an analog of the paracoumaric acid chromophore

The low-lying excited singlet states of paravinyl phenol (pVP) are investigated experimentally and theoretically paying attention to their similarity to excited states of paracoumaric acid, the chromophore of the photoactive yellow protein (PYP). Resonance enhanced multiphoton ionization and laser induced fluorescence spectroscopic techniques are employed to obtain supersonically cooled, vibrationally resolved excitation and emission spectra related to the lowest (1)A'(V') excited state of pVP. Comprehensive analyses of the spectral structures are carried out by means of the equation-of-motion coupled cluster singles and doubles and time dependent density functional theory methods in combination with the linear vibronic coupling model and Franck-Condon calculations. The assignments of the spectral patterns are given, mostly in terms of excitations of totally symmetric modes. Weak activity of the non-totally-symmetric modes indicates low probability of photochemical processes in the Franck-Condon region of the (1)A'(V') state. The second (1)A'(V) and third (1)A" (Ryd) excited states of pVP are characterized with regard to their electronic structure, properties, and effects of geometry relaxations. The lengthening of the double bond relevant to the trans-cis isomerization of the PYP chromophore is found for the (1)A'(V) state. A possibility of photochemical processes and strong vibronic interactions in this state can be expected. The theoretical results for the (1)A"(Ryd) state predict that dissociation with respect to the O-H bond is possible.     

Interatomic decay of inner-valence-excited states in clusters

In an isolated atom, excitation of an inner valence electron above the outer valence subshell leads to creation of an autoionizing state. Recently, it has been demonstrated experimentally that in a cluster, the inner-valence-excited states can decay also by an interatomic mechanism which has been called resonant interatomic Coulombic decay (RICD). Here we show that RICD is indeed the leading but not the only possible interatomic decay mode of the inner-valence excitations in clusters. Using Ne (2s-->3p) excitation in MgNe cluster as an example, we explore the possible decay mechanisms and draw conclusions on their relative importance and on the nature of the corresponding decay products.     

Short-time dynamics through conical intersections in macrosystems. I. Theory: effective-mode formulation

The short-time dynamics through a conical intersection of a macrosystem comprising a large number of nuclear degrees of freedom (modes) is investigated. The macrosystem is decomposed into a "system" part carrying a limited number of modes, and an "environment" part. An orthogonal transformation in the environment's space is introduced, as a result of which a subset of three effective modes can be identified which couple directly to the electronic subsystem. Together with the system's modes, these govern the short-time dynamics of the overall macrosystem. The remaining environmental modes couple, in turn, to the effective modes and become relevant at longer times. In this paper, we present the derivation of the effective Hamiltonian, first introduced by Cederbaum et al. [Phys. Rev. Lett. 94, 113003 (2005)], and analyze its properties in some detail. Several special cases and topological aspects are discussed.     

Particle-number-dependent theory of few- and many-body systems

The introduction of approximations to evaluate physical properties of few- or many-body systems may violate exact symmetries and conservation laws. If, for example, the numberN of particles is incorrectly reproduced by the approximation, it can be shown that the optical potential for scattering of charged particles exhibits a spurious long-range potential. It is suggested to correct forN by introducing a particle-number-dependent interaction into the Hamiltonian, which does not influence exact results but changes the results of the approximation. The interaction is such that the original working equations of the approximation scheme undergo a trivial change only. As an example a simple model is investigated. It is found that restoringN also substantially improves all observables of the system.     

Strongly magnetized antihydrogen and its field ionization

Internal orbits of experimentally analyzed antihydrogen (H) atoms depend as much on an external magnetic field as on the Coulomb force. A circular "guiding center atom" model is used to understand their field ionization. This useful model, assumed in the theory of three-body H recombination so far, ignores the important coupling between internal and center-of-mass motion. A conserved pseudomomentum, effective potential, saddle point analysis, and numerical simulation show where the simple model is valid and classify the features of the general case, including "giant dipole states."     

Quantum states of magnetically induced anions

In a magnetic field, an atom (or molecule) can attach an extra electron to form an unconventional anionic state which has no counterparts in field-free space. Assuming the atom to be infinitely heavy, these magnetically induced anionic states are known to constitute an infinite manifold of bound states. In reality, the species can move and its motion across the magnetic field couples to the motion of the attached electron. We treat this coupling, for the first time, quantum mechanically, and show that it makes the number of bound anionic states finite. Explicit numerical quantum results are presented and discussed.