Impact of Structure, Coupling Scheme, and State of Interest on the Energy Transfer in CP29.

The Qy and Bx excitation energy transfer (EET) in the minor light-harvesting complex CP29 (LHCII B4.1) antenna complex of Pisum sativum was characterized using a computational approach. We applied Förster resonance energy transfer (FRET) and the transition density cube (TDC) method to estimate the Coulombic coupling, based on a combination of classical molecular dynamics and quantum mechanics/molecular mechanics calculations. Employing TDC instead of FRET mostly affects the EET between chlorophylls (Chls) and carotenoids (Crts), as expected due to the Crts being spatially more challenging for FRET. Only between Chls, effects are found to be small (about only 0.1 EET efficiency change when introducing TDC instead of FRET). Effects of structural sampling were found to be small, illustrated by a small average standard deviation for the Qy state coupling elements (FRET/TDC: 0.97/0.94 cm-1). Due to the higher flexibility of the Bx state, the corresponding deviations are larger (FRET/TDC between Chl-Chl pairs: 17.58/22.67 cm-1, between Crt-Chl pairs: 62.58/31.63 cm-1). In summary, it was found for the Q band that the coupling between Chls varies only slightly depending on FRET or TDC, resulting in a minute effect on EET acceptor preference. In contrast, the coupling in the B band spectral region is found to be more affected. Here, the S2 (1Bu) states of the spatially challenging Crts may act as acceptors in addition to the B states of the Chls. Depending on FRET or TDC, several Chls show different Chl-to-Crt couplings. Interestingly, the EET between Chls or Crts in the B band is found to often outcompete the corresponding decay processes. The individual efficiencies for B band EET to Crts vary however strongly with the chosen coupling scheme (e.g., up to 0.29/0.99 FRET/TDC efficiency for the Chl a604/neoxanthin pair). Thus, the choice of the coupling scheme must involve a consideration of the state of interest.

Is it really possible to control aromaticity of benzene with light?

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 Kekulé 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 (D6h) 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 Kekulé resonance structures.

Stochastic wave packet approach to nonadiabatic scattering of diatomic molecules from metals.

In this contribution, we present a quantum dynamical approach to study inelastic scattering of diatomic molecules from metal surfaces at normal incidence. The dissipative dynamics obeys a stochastic Schrödinger equation describing the time-evolution of the system as a piecewise deterministic process. Energy exchange between the molecular vibrational degrees of freedom and the metal electrons is represented using operators in tensor product form, which are coupled via anharmonic transition rates calculated from first-order perturbation theory. Full dimensional observables are obtained by averaging over simulations in 4D-including the internal stretch, the distance to the surface, and the orientation angles-at different surface sites. The method is applied to the state-resolved scattering of vibrationally excited NO from Au(111), revealing important channels for quantized energy relaxation.

Ultrafast Transient Dynamics of Adsorbates on Surfaces Deciphered: The Case of CO on Cu(100).

Time-resolved vibrational spectroscopy constitutes an invaluable experimental tool for monitoring hot-carrier-induced surface reactions. However, the absence of a full understanding of the precise microscopic mechanisms causing the transient spectral changes has limited its applicability. Here we introduce a robust first-principles theoretical framework that successfully explains both the nonthermal frequency and linewidth changes of the CO internal stretch mode on Cu(100) induced by femtosecond laser pulses. Two distinct processes engender the changes: electron-hole pair excitations underlie the nonthermal frequency shifts, while electron-mediated vibrational mode coupling gives rise to linewidth changes. Furthermore, the origin and precise sequence of coupling events are finally identified.

Ultrafast photoelectron migration in dye-sensitized solar cells: Influence of the binding mode and many-body interactions.

In the present contribution, the ultrafast photoinduced electron migration dynamics at the interface between an alizarin dye and an anatase TiO2 thin film is investigated from first principles. Comparison between a time-dependent many-electron configuration interaction ansatz and a single active electron approach sheds light on the importance of many-body effects, stemming from uniquely defined initial conditions prior to photoexcitation. Particular emphasis is put on understanding the influence of the binding mode on the migration process. The dynamics is analyzed on the basis of a recently introduced toolset in the form of electron yields, electronic fluxes, and flux densities, to reveal microscopic details of the electron migration mechanism. From the many-body perspective, insight into the nature of electron-electron and hole-hole interactions during the charge transfer process is obtained. The present results reveal that the single active electron approach yields quantitatively and phenomenologically similar results as the many-electron ansatz. Furthermore, the charge migration processes in the dye-TiO2 model clusters with different binding modes exhibit similar mechanistic pathways but on largely different time scales.

Diffusion of hydrogen interstitials in the near-surface region of Pd(111) under the influence of surface coverage and external static electric fields.

Past scanning tunneling microscopy (STM) experiments of H manipulation on Pd(111), at low temperature, have shown that it is possible to induce diffusion of surface species as well as of those deeply buried under the surface. Several questions remain open regarding the role of subsurface site occupancies. In the present work, the interaction potential of H atoms with Pd(111) under various H coverage conditions is determined by means of density functional theory calculations in order to provide an answer to two of these questions: (i) whether subsurface sites are the final locations for the H impurities that attempt to emerge from bulk regions, and (ii) whether penetration of the surface is a competing route of on-surface diffusion during depletion of surface H on densely covered Pd(111). We find that a high H coverage has the effect of blocking resurfacing of H atoms travelling from below, which would otherwise reach the surface fcc sites, but it hardly alters deeper diffusion energy barriers. Penetration is unlikely and restricted to high occupancies of hcp hollows. In agreement with experiments, the Pd lattice expands vertically as a consequence of H atoms being blocked at subsurface sites, and surface H enhances this expansion. STM tip effects are included in the calculations self-consistently as an external static electric field. The main contribution to the induced surface electric dipoles originates from the Pd substrate polarisability. We find that the electric field has a non-negligible effect on the H-Pd potential in the vicinity of the topmost Pd atomic layer, yet typical STM intensities of 1-2 VÅ(-1) are insufficient to invert the stabilities of the surface and subsurface equilibrium sites.

Relaxation dynamics in quantum dissipative systems: the microscopic effect of intramolecular vibrational energy redistribution.

We investigate the effect of inter-mode coupling on the vibrational relaxation dynamics of molecules in weak dissipative environments. The simulations are performed within the reduced density matrix formalism in the Markovian regime, assuming a Lindblad form for the system-bath interaction. The prototypical two-dimensional model system representing two CO molecules approaching a Cu(100) surface is adapted from an ab initio potential, while the diatom-diatom vibrational coupling strength is systematically varied. In the weak system-bath coupling limit and at low temperatures, only first order non-adiabatic uni-modal coupling terms contribute to surface-mediated vibrational relaxation. Since dissipative dynamics is non-unitary, the choice of representation will affect the evolution of the reduced density matrix. Two alternative representations for computing the relaxation rates and the associated operators are thus compared: the fully coupled spectral basis, and a factorizable ansatz. The former is well-established and serves as a benchmark for the solution of Liouville-von Neumann equation. In the latter, a contracted grid basis of potential-optimized discrete variable representation is tailored to incorporate most of the inter-mode coupling, while the Lindblad operators are represented as tensor products of one-dimensional operators, for consistency. This procedure results in a marked reduction of the grid size and in a much more advantageous scaling of the computational cost with respect to the increase of the dimensionality of the system. The factorizable method is found to provide an accurate description of the dissipative quantum dynamics of the model system, specifically of the time evolution of the state populations and of the probability density distribution of the molecular wave packet. The influence of intra-molecular vibrational energy redistribution appears to be properly taken into account by the new model on the whole range of coupling strengths. It demontrates that most of the mode mixing during relaxation is due to the potential part of the Hamiltonian and not to the coupling among relaxation operators.

Concept of a single temperature for highly nonequilibrium laser-induced hydrogen desorption from a ruthenium surface.

Laser-induced condensed phase reactions are often interpreted as nonequilibrium phenomena that go beyond conventional thermodynamics. Here, we show by Langevin dynamics and for the example of femtosecond-laser desorption of hydrogen from a ruthenium surface that light adsorbates thermalize rapidly due to ultrafast energy redistribution after laser excitation. Despite the complex reaction mechanism involving hot electrons in the surface region, all desorption product properties are characterized by equilibrium distributions associated with a single, unique temperature. This represents an example of ultrahot chemistry on the subpicosecond time scale.