One dimensional cuts through multidimensional potential energy surfaces by tunable x rays

The concept of the potential energy surface PES and directional reaction coordinates is the backbone of our description of chemical reaction mechanisms. Although the eigenenergies of the nuclear Hamiltonian uniquely link a PES to its spectrum, this information is in general experimentally inaccessible in large polyatomic systems. This is due to near degenerate rovibrational levels across the parameter space of all degrees of freedom, which effectively forms a pseudospectrum given by the centers of gravity of groups of close lying vibrational levels. We show here that resonant inelastic x ray scattering RIXS constitutes an ideal probe for revealing one dimensional cuts through the ground state PES of molecular systems, even far away from the equilibrium geometry, where the independent mode picture is broken. We strictly link the center of gravity of close lying vibrational peaks in RIXS to a pseudospectrum which is shown to coincide with the eigenvalues of an effective one dimensional Hamiltonian along the propagation coordinate of the core excited wave packet. This concept, combined with directional and site selectivity of the core excited states, allows us to experimentally extract cuts through the ground state PES along three complementary directions for the showcase H2O molecul

Origin of Long Lived Coherences in Light-Harvesting Complexes

A vibronic exciton model is developed to investigate the origin of long lived coherences in light-harvesting complexes. Using experimentally determined parameters and uncorrelated site energy fluctuations, the model predicts oscillations in the nonlinear spectra of the Fenna-Matthews-Olson (FMO) complex with a dephasing time of 1.3 ps at 77 K. These oscillations correspond to the coherent superposition of vibronic exciton states with dominant contributions from vibrational excitations on the same pigment. Purely electronic coherences are found to decay on a 200 fs timescale.Comment: 4 pages, 2 figure

Nuclear dynamics in resonant inelastic X-ray scattering and X-ray absorption of methanol

We report on a combined theoretical and experimental study of core-excitation spectra of gas and liquid phase methanol as obtained with the use of X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS). The electronic transitions are studied with computational methods that include strict and extended second-order algebraic diagrammatic construction [ADC(2) and ADC(2)-x], restricted active space second-order perturbation theory, and time-dependent density functional theory-providing a complete assignment of the near oxygen K-edge XAS. We show that multimode nuclear dynamics is of crucial importance for explaining the available experimental XAS and RIXS spectra. The multimode nuclear motion was considered in a recently developed "mixed representation" where dissociative states and highly excited vibrational modes are accurately treated with a time-dependent wave packet technique, while the remaining active vibrational modes are described using Franck-Condon amplitudes. Particular attention is paid to the polarization dependence of RIXS and the effects of the isotopic substitution on the RIXS profile in the case of dissociative core-excited states. Our approach predicts the splitting of the 2a RIXS peak to be due to an interplay between molecular and pseudo-atomic features arising in the course of transitions between dissociative core- and valence-excited states. The dynamical nature of the splitting of the 2a peak in RIXS of liquid methanol near pre-edge core excitation is shown. The theoretical results are in good agreement with our liquid phase measurements and gas phase experimental data available from the literature. (C) 2019 Author(s)

Restructuring of plasmonic nanoparticle aggregates with arbitrary particle size distribution in pulsed laser fields

We have studied processes of interaction of pulsed laser radiation with resonant groups of plasmonic nanoparticles (resonant domains) in large colloidal nanoparticle aggregates having different interparticle gaps and particle size distributions. These processes are responsible for the origin of nonlinear optical effects and photochromic reactions in multiparticle aggregates. To describe photo-induced transformations in resonant domains and alterations in their absorption spectra remaining after the pulse action, we introduce the factor of spectral photomodification. Based on calculation of changes in thermodynamic, mechanical, and optical characteristics of the domains, the histograms of the spectrum photomodification factor have been obtained for various interparticle gaps, an average particle size, and the degree of polydispersity. Variations in spectra have been analyzed depending on the intensity of laser radiation and various combinations of size characteristics of domains. The obtained results can be used to predict manifestation of photochromic effects in composite materials containing different plasmonic nanoparticle aggregates in pulsed laser fields

Optimization of photothermal methods for laser hyperthermia of malignant cells using bioconjugates of gold nanoparticles

Selective action of laser radiation on membranes of malignant cells has been studied in different regimes using conjugates of gold nanoparticles with oligonucleotides by the example of DNA aptamers. Under the conditions of a contact between a bioconjugate and a cell surface and the development of substantial and rapidly relaxing temperature gradients near a nanoparticle, the membranes of malignant cells alone are efficiently damaged due to the local hyperthermia of a cellular membrane. It has been shown that employment of pulsed instead of continuous wave laser radiation provides the localization of the damaging action, which does not involve healthy cells

Restructuring of plasmonic nanoparticle aggregates with arbitrary particle size distribution in pulsed laser fields

We have studied processes of interaction of pulsed laser radiation with resonant groups of plasmonic nanoparticles (resonant domains) in large colloidal nanoparticle aggregates having different interparticle gaps and particle size distributions. These processes are responsible for the origin of nonlinear optical effects and photochromic reactions in multiparticle aggregates. To describe photo-induced transformations in resonant domains and alterations in their absorption spectra remaining after the pulse action, we introduce the factor of spectral photomodification. Based on calculation of changes in thermodynamic, mechanical, and optical characteristics of the domains, the histograms of the spectrum photomodification factor have been obtained for various interparticle gaps, an average particle size, and the degree of polydispersity. Variations in spectra have been analyzed depending on the intensity of laser radiation and various combinations of size characteristics of domains. The obtained results can be used to predict manifestation of photochromic effects in composite materials containing different plasmonic nanoparticle aggregates in pulsed laser fields

Charge transfer plasmons in the arrays of nanoparticles connected by conductive linkers

Charge transfer plasmons (CTPs) that occur in different topology and dimensionality arrays of metallic nanoparticles (NPs) linked by narrow molecular bridges are studied. The occurrence of CTPs in such arrays is related to the ballistic motion of electrons in thin linkers with the conductivity that is purely imaginary, in contrast to the case of conventional CTPs, where metallic NPs are linked by thick bridges with the real optical conductivity caused by carrier scattering. An original hybrid model for describing the CTPs with such linkers has been further developed. For different NP arrays, either a general analytical expression or a numerical solution has been obtained for the CTP frequencies. It has been shown that the CTP frequencies lie in the IR spectral range and depend on both the linker conductivity and the system geometry. It is found that the electron currents of plasmon oscillations correspond to minor charge displacements of only few electrons. It has been established that the interaction of the CTPs with an external electromagnetic field strongly depends on the symmetry of the electron currents in the linkers, which, in turn, are fully governed by the symmetry of the investigated system. The extended model and the analytical expressions for the CTPs frequencies have been compared with the conventional finite difference time domain simulations. It is argued that applications of this novel type of plasmon may have wide ramifications in the area of chemical sensing