Migration of Excitation Energy in Furocoumarins

The migration of excitation energy of a number of psoralen compounds has been studied. For this, the methods of induced absorption spectroscopy, stationary electron spectroscopy, fluorescence and phosphorescence, as well as quantum chemistry were used. A comparative photostability of psoralen was achieved by exposure to a XeCl excilamp irradiation (emission wavelength λem = 308 nm) with parameters Δλ = 5–10 nm, Wpeak = 18 mW/cm2, p = 8.1 J/cm3, f = 200 kHz, pulse duration 1 μs. It was found that the singlet-triplet transition played a major role in the migration of excitation energy into triplet states. Among all tested compounds, substances with an OCH3-group in the structure have the strongest effect on the spectral-luminescent characteristics.

Ultrafast intersystem crossing in xanthone from wavepacket dynamics simulations

Most aromatic ketones containing first-row elements undergo unexpectedly fast intersystem crossing in few tens of picosecond and a quantum yield close to unity. Among them, xanthone (9H-xanthen-9-one) possesses one of the fastest intersystem crossing rates of ~1.5 ps, despite containing only first-row elements. The exact mechanism of this unusually fast singlet-triplet transition is still under debate. Here, we perform a complete wavepacket dynamics simulation of the internal conversion and intersystem crossing reactions of xanthone in the gas phase. We show that xanthone follows El-Sayed's rule for intersystem crossing. From the second singlet excited state, the mechanism is sequential: (i) an internal conversion between singlets 1pipi*-1npi* (~0.14 fs), (ii) an intersystem crossing 1npi*-3pipi* (~1.8 ps), and (iii) an internal conversion between triplets 3pipi*-3npi* (~27 ps). Each transfer finds its origin in a barrierless access to electronic state intersections. These intersections are close to minimum energy structures, allowing for an efficient radiationless transition from 1pipi* to 3npi*.

On the Stark Effect of the O I 777-nm Triplet in Plasma and Laser Fields

The O I 777-nm triplet transition is often used for plasma density diagnostics. It is also employed in nonlinear optics setups for producing quasi-comb structures when pumped by a near-resonant laser field. Here, we apply computer simulations to situations of the radiating atom subjected to the plasma microfields, laser fields, and both perturbations together. Our results, in particular, resolve a controversy related to the spectral line anomalously broadened in some laser-produced plasmas. The importance of using time-dependent density matrix is discussed.

Direct population of triplet excited states through singlet–triplet transition for visible-light excitable organic afterglow

Direct population of triplet states via singlet-to-triplet absorption red-shifts the excitation wavelength and improves the organic afterglow efficiency under ambient conditions.