Two-color four-wave mixing contribution to an electrostrictive laser-induced grating signal in CO2-N2 mixtures and gas diagnostics: publisher's note.

This publisher's note corrects content in Appl. Opt.62, 8115 (2023)APOPAI0003-693510.1364/AO.497467.

Two-color four-wave mixing contribution to an electrostrictive laser-induced grating signal in CO2-N2 mixtures and gas diagnostics.

Multiparameter determination in the gas phase using the versatile laser-induced grating (LIG) technique is a challenging task due to interdependence of observables on multiple thermodynamic parameters. In C O 2-N 2 mixtures, simultaneous determination of species concentration and gas temperature can be achieved by using an additional C O 2 concentration-dependent contribution to the LIG signal, which appears if 1064 nm pump pulses are employed. This contribution can be attributed to a direct, quasi-resonant two-color four-wave mixing (TCFWM) of the pump and probe radiations in C O 2. A detailed study of the laser power and beam polarization, as well as mixture composition, pressure, and temperature dependencies of the TCFWM intensity relative to that of the LIG signal, allowed for the formulation of analytical relations enabling simultaneous mixture composition and temperature determination.

Improvement of the coherent model function for S-branch Raman linewidth determination in oxygen.

Determination of S-branch Raman linewidths of oxygen from picosecond time-domain pure rotational coherent anti-Stokes Raman spectroscopy (RCARS) measurements requires consideration of coherence beating. We present an optimization of the established model for fitting the coherence decay in oxygen, which leads to an improvement in Raman linewidth data quality, especially for the challenging small signal intensity and decay constant regime, enabling the application for low oxygen concentrations. Two modifications to the fitting procedure are discussed, which aim at reliably fitting the second coherence beat properly. These are evaluated statistically against simulated decay traces, and weighing the data by the inverse of the data magnitude gives the best agreement. The presented temperature dependent ${{\rm O}_2} {-} {{\rm O}_2}$ S-branch Raman linewidth from the modified model shows an improved data quality over the original model function for all studied temperatures. ${{\rm O}_2} {-} {{\rm N}_2}$ linewidths of oxygen in air for the temperature range from 295 K to 1900 K demonstrate applicability to small concentrations. Use of the determined RCARS ${{\rm O}_2} {-} {{\rm O}_2}$ S-branch linewidth instead of regularly used Q-branch derived linewidths leads to a lowering in evaluated RCARS temperature by about 21 K, thereby, a much better agreement with thermocouple measurements.

Temperature dependent determination of the S-branch Raman linewidths of oxygen and carbon dioxide in an oxyfuel relevant mixture.

The temperature dependence of the ${\rm O}_2$ and ${\rm CO}_2$ S-branch linewidths in a 30/70% ${\rm O}_2 - {\rm CO}_2$ mixture between 295 K and 1900 K has been studied by a picosecond time-resolved pure rotational coherent anti-Stokes Raman scattering (RCARS) approach. The S-branch Raman linewidths are required for diagnostics of thermodynamic properties in oxyfuel combustion processes by RCARS, where this mixture is of special interest, because it is regularly used to replace air when transiting from air-fed to oxyfuel combustion. The obtained linewidths for oxygen and carbon dioxide show a strong deviation from pure self-broadened linewidths and previously used Q-branch linewidths, respectively. A discussion on the expected impact on RCARS thermometry and concentration evaluations as well as a description of specific properties of oxygen and carbon dioxide and their effect on the dephasing behavior of the Raman coherences and, thereby the Raman linewidths, is included, along tabulated linewidths data of both molecules.

Determination of N2-N2 and N2-O2 S-branch Raman linewidths using time-resolved picosecond pure rotational coherent anti-Stokes Raman scattering.

N2-N2 and N2-O2 S-branch Raman linewidths have been determined using picosecond dual-broadband pure rotational coherent anti-Stokes Raman scattering (CARS). Time-resolved rotational CARS measurements were performed in gas-phase N2 and air for temperatures up to 1900 K in order to determine the time constants of the coherence decay to subsequently calculate the S-branch Raman linewidths. Coherence decay time traces and the resulting S-branch Raman linewidths are presented for N2-N2 and N2-O2 collisions. Therewith, we reduce the gap of widely missing S-branch linewidth data in the temperature regime of many combustion processes. Further, we demonstrate that the standard monoexponential fitting of the coherence decay, as it is commonly done for nitrogen, is not applicable to oxygen.

A comprehensive picture of the ultrafast excited-state dynamics of retinal.

All-trans retinal is the chromophore of microbial rhodopsins initiating energy conversion and cellular signalling by subpicosecond photoinduced switching. Here, we provide detailed UV-Vis transient absorption experiments to disentangle the complex photochemistry of this polyene, which is governed by its terminal aldehyde group. After photoexcitation to the S2((1)Bu(+)) state, the system exhibits polarity-dependent branching, populating separate S1((1)Ag(-)) and intramolecular charge transfer (ICT) species. In all solvents, population of a singlet nπ* state from S1 is observed which represents the precursor of the T1 triplet state. While triplet formation dominates in nonpolar solvents (67% quantum yield), it is dramatically reduced in polar solvents (4%). The channel closes completely upon replacing the aldehyde by a carboxyl group, due to an energetic up-shift of (1)nπ*. In that case, internal conversion via the ICT species becomes the main pathway, with preferential formation of the initially excited isomer.