Absorption and Circular Dichroism Spectra of Molecular Aggregates with the Full Cumulant Expansion.

The exciton Hamiltonian of multichromophoric aggregates can be probed by spectroscopic techniques such as linear absorption and circular dichroism. In order to compare calculated Hamiltonians to experiments, a lineshape theory is needed, which takes into account the coupling of the excitons with inter- and intramolecular vibrations. This coupling is normally introduced in a perturbative way through the cumulant expansion formalism, and further approximated by assuming a Markovian exciton dynamics, for example with the modified Redfield theory.<br><br>Here we present an implementation of the full cumulant expansion (FCE) formalism [Ma and Cao, <i>J. Chem. Phys.</i> <b>2015</b>, 142, 094106 ] to efficiently compute absorption and circular dichroism spectra of molecular aggregates beyond the Markov approximation, without restrictions on the form of the exciton-phonon coupling. By employing the LH2 system of purple bacteria as a challenging test case, we compare the FCE lineshapes with the Markovian lineshapes obtained with the modified Redfield theory, showing that the latter present a much poorer agreement with experiments. The FCE approach instead accurately describes the lineshapes, especially in the vibronic sideband of the B800 peak. We envision that the FCE approach will become a valuable tool for accurately comparing model exciton Hamiltonians with optical spectroscopy experiments.

Absorption and Circular Dichroism Spectra of Molecular Aggregates with the Full Cumulant Expansion.

The exciton Hamiltonian of multichromophoric aggregates can be probed by spectroscopic techniques such as linear absorption and circular dichroism. In order to compare calculated Hamiltonians to experiments, a lineshape theory is needed, which takes into account the coupling of the excitons with inter- and intramolecular vibrations. This coupling is normally introduced in a perturbative way through the cumulant expansion formalism, and further approximated by assuming a Markovian exciton dynamics, for example with the modified Redfield theory.<br><br>Here we present an implementation of the full cumulant expansion (FCE) formalism [Ma and Cao, <i>J. Chem. Phys.</i> <b>2015</b>, 142, 094106 ] to efficiently compute absorption and circular dichroism spectra of molecular aggregates beyond the Markov approximation, without restrictions on the form of the exciton-phonon coupling. By employing the LH2 system of purple bacteria as a challenging test case, we compare the FCE lineshapes with the Markovian lineshapes obtained with the modified Redfield theory, showing that the latter present a much poorer agreement with experiments. The FCE approach instead accurately describes the lineshapes, especially in the vibronic sideband of the B800 peak. We envision that the FCE approach will become a valuable tool for accurately comparing model exciton Hamiltonians with optical spectroscopy experiments.

Nickel-Silicon Related Color Center Formed in Nanodiamond Grains under CVD Growth

Formation of optical centers in nanodiamond grains with narrow, near-infrared emission at room temperature is one of the most important challenges nowadays. Our aim was to form a metal-related color center through the CVD growth process of nanodiamond. Previously undocumented photoluminescence (PL) system with 865 nm zero-phonon line (ZPL) and 2 nm full width at half maximum (FWHM) was successfully created in nanodiamond grains. According to the detailed analysis of the spectral features of the ZPL and quasilocal modes of the vibronic sideband, a complex center containing Ni and Si atoms could be accounted for these PL features. The inclusion of Ni and Si impurity atoms in the complex optical center was strengthened by micro-Raman spectroscopy performed in the frequency range due to quasilocal vibrations of the vibronic sideband.

Optical Characterization of Europium-Doped Calcium Fluoride Thin Films Grown on Silicon by Molecular Beam Epitaxy

Photoluminescence measurements have been made on Eu-doped CaF2 thin films grown on Si(100) substrates. The dependence of the integrated intensity of both the zero-phonon line and the vibronic sideband on temperature and Eu concentration has been studied in the range of 10 – 300 K and 0.14 – 7.48 at. %, respectively. An anti-Stokes feature is visible in the emission spectra at 75 K, indicating a significant occupation of the excited vibrational states of Eu2+ by phonons before the transition at temperatures above 75 K. The integrated intensity of the vibronic sideband increases slightly as temperature increases. The solubility of Eu in CaF2 thin films grown on Si(100) is found to be somewhere around 4.05 at. % as confirmed by the increase of the line width of x-ray rocking curves and the decrease in the integrated intensity of the zero-phonon line with Eu concentration.