@article{FischerWertherBouaklineetal.2020,
  author    = {Fischer, Eric W. and Werther, Michael and Bouakline, Foudhil and Saalfrank, Peter},
  title     = {A hierarchical effective mode approach to phonon-driven multilevel vibrational relaxation dynamics at surfaces},
  series = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistry},
  volume    = {153},
  journal   = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistry},
  number    = {6},
  publisher = {American Institute of Physics},
  address   = {Melville},
  issn      = {0021-9606},
  doi       = {10.1063/5.0017716},
  pages     = {15},
  year      = {2020},
  abstract  = {We discuss an efficient Hierarchical Effective Mode (HEM) representation of a high-dimensional harmonic oscillator bath, which describes phonon-driven vibrational relaxation of an adsorbate-surface system, namely, deuterium adsorbed on Si(100). Starting from the original Hamiltonian of the adsorbate-surface system, the HEM representation is constructed via iterative orthogonal transformations, which are efficiently implemented with Householder matrices. The detailed description of the HEM representation and its construction are given in the second quantization representation. The hierarchical nature of this representation allows access to the exact quantum dynamics of the adsorbate-surface system over finite time intervals, controllable via the truncation order of the hierarchy. To study the convergence properties of the effective mode representation, we solve the time-dependent Schrodinger equation of the truncated system-bath HEM Hamiltonian, with the help of the multilayer extension of the Multiconfigurational Time-Dependent Hartree (ML-MCTDH) method. The results of the HEM representation are compared with those obtained with a quantum-mechanical tier-model. The convergence of the HEM representation with respect to the truncation order of the hierarchy is discussed for different initial conditions of the adsorbate-surface system. The combination of the HEM representation with the ML-MCTDH method provides information on the time evolution of the system (adsorbate) and multiple effective modes of the bath (surface). This permits insight into mechanisms of vibration-phonon coupling of the adsorbate-surface system, as well as inter-mode couplings of the effective bath.},
  language  = {en}
}
@article{Bouakline2020,
  author    = {Bouakline, Foudhil},
  title     = {Does nuclear permutation symmetry allow dynamical localization in symmetric double-well achiral molecules?},
  series = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr},
  volume    = {152},
  journal   = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr},
  number    = {24},
  publisher = {American Institute of Physics},
  address   = {Melville},
  issn      = {0021-9606},
  doi       = {10.1063/1.5141746},
  pages     = {17},
  year      = {2020},
  abstract  = {We discuss the effect of molecular symmetry on coherent tunneling in symmetric double-well potentials whose two molecular equilibrium configurations are interconverted by nuclear permutations. This is illustrated with vibrational tunneling in ammonia molecules, electronic tunneling in the dihydrogen cation, and laser-induced rotational tunneling of homonuclear diatomics. In this contribution, we reexamine the textbook picture of coherent tunneling in such potentials, which is depicted with a wavepacket shuttling back and forth between the two potential-wells. We show that the common application of this picture to the aforementioned molecules contravenes the principle of the indistinguishability of identical particles. This conflict originates from the sole consideration of the dynamics of the tunneling-mode, connecting the double-well energy minima, and complete omission of all the remaining molecular degrees of freedom. This gives rise to double-well wavepackets that are nonsymmetric under nuclear permutations. To obey quantum statistics, we show that the double-well eigenstates composing these wavepackets must be entangled with the wavefunctions that describe all the omitted molecular modes. These wavefunctions have compensating and opposite nuclear permutation symmetry. This in turn leads to complete quenching of interference effects behind localization in one potential-well or another. Indeed, we demonstrate that the reduced density of probability of the symmetrized molecular wavefunction, where all the molecular coordinates but the tunneling-mode are integrated out, is symmetrically distributed over the two potential-wells, at all times. This applies to any multilevel wavepacket of isotropic or fully aligned symmetric double-well achiral molecules. However, in the case of coherent electronic or vibrational tunneling, fully aligned molecules may exhibit dynamical localization in the space-fixed frame, where the tunneling-mode density shuttles between the opposite directions of the alignment axis. This dynamical spatial-localization results from linear combinations of molecular states that have opposite parity. In summary, this study shows that dynamical localization of the tunneling-mode density on either of the two indistinguishable molecular equilibrium configurations of symmetric double-well achiral molecules is forbidden by quantum statistics, whereas its dynamical localization in the space-fixed frame is allowed by parity. The subtle distinction between these two types of localization has far-reaching implications in the interpretation of many ultrafast molecular dynamics experiments.},
  language  = {en}
}
@article{BouaklineTremblay2020,
  author    = {Bouakline, Foudhil and Tremblay, Jean Christophe},
  title     = {Is it really possible to control aromaticity of benzene with light?},
  series = {Physical chemistry, chemical physics : PCCP},
  volume    = {22},
  journal   = {Physical chemistry, chemical physics : PCCP},
  number    = {27},
  publisher = {Royal Society of Chemistry},
  address   = {Cambridge},
  issn      = {1463-9076},
  doi       = {10.1039/c9cp06794a},
  pages     = {15401 -- 15412},
  year      = {2020},
  abstract  = {Recent theoretical investigations claim that tailored laser pulses may selectively steer benzene's aromatic ground state to localized non-aromatic excited states. For instance, it has been shown that electronic wavepackets, involving the two lowest electronic eigenstates, exhibit subfemtosecond charge oscillation between equivalent Kekule resonance structures. In this contribution, we show that such dynamical electron-localization in the molecule-fixed frame contravenes the principle of the indistinguishability of identical particles. This breach stems from a total omission of the nuclear degrees of freedom, giving rise to nonsymmetric electronic wavepackets under nuclear permutations. Enforcement of the latter leads to entanglement between the electronic and nuclear states. To obey quantum statistics, the entangled molecular states should involve compensating nuclear-permutation symmetries. This in turn engenders complete quenching of dynamical electron-localization in the molecule-fixed frame. Indeed, for the (six-fold) equilibrium geometry of benzene, group-theoretic analysis reveals that any electronic wavepacket exhibits a (D-6h) totally symmetric electronic density, at all times. Thus, our results clearly show that the six carbon atoms, and the six C-C bonds, always have equal Mulliken charges, and equal bond orders, respectively. However, electronic wavepackets may display dynamical localization of the electronic density in the space-fixed frame, whenever they involve both even and odd space-inversion (parity) or permutation-inversion symmetry. Dynamical spatial-localization can be probed experimentally in the laboratory frame, but it should not be deemed equivalent to charge oscillation between benzene's identical electronic substructures, such as Kekule resonance structures.},
  language  = {en}
}