Determination of Secondary Species in Solution through Pump-Selective Transient Absorption Spectroscopy and Explicit-Solvent TDDFT

Abstract

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Exploring the Photochemistry of an Ethyl Sinapate Dimer: An Attempt Toward a Better Ultraviolet Filter

“…Owing to this, the predicted energies for these species, as well as predicted vertical excitation energies, are presented as an approximation of each form rather than as quantitative data. Furthermore, the effect of explicit solvent interactions are not captured by our technique, these likely also have an effect on the relative energies of the species (Zuehlsdorff et al, 2017 ; Turner et al, 2019 ). Additionally, the two isomers display several significant differences in geometry, beyond just isomerization around the double bonds.…”

Unravelling photoprotection in microbial natural products

“…44,45 However, to fully capture the explicit nature of solvent interaction and systems such as those described above, particularly hydrogen bonding for example, multiple solvation shells are regularly required along with one of the aforementioned models to achieve suitable levels of accuracy. [46][47][48] Ab-initio methods make use of self-consistent field (SCF) methods and Hartree-Fock Slater determinants, to define a full wavefunction for the system using a set of given orbitals and a prescribed number of electrons. A particular approach, known as complete active space selfconsistent field (CASSCF), has advantages in finding degeneracies between excited states, so called conical intersections (CI), which often drive non-radiative relaxation of the excited state population (crucial for an effective sunscreen filter, as will be discussed later).…”

“…44,45 However, to fully capture the explicit nature of solvent interaction and systems such as those described above, particularly hydrogen bonding, for example, multiple solvation shells are regularly required along with one of the aforementioned models to achieve suitable levels of accuracy. 46–48…”

Ultrafast transient absorption spectroelectrochemistry: femtosecond to nanosecond excited-state relaxation dynamics of the individual components of an anthraquinone redox couple

“…Calculations were performed with ESTEEM. [51][52][53] Initial geometry optimisations and DFT and TDDFT ground and excited state calculations [54][55][56][57][58] on the isolated systems (gas phase, then implicit water solvent) were performed with the NWChem Package. We test a range of functionals, namely LC-uPBE, PBE, PBE0, LC-PBE0, and CAM-B3LYP, in order to understand the molecular structures and the energy levels involved in their photoexcitation.…”

“…The triplet state vertical excitation energies in the Franck-Condon region, albeit less reliable, are indicative of a triplet state T n with energy below the rst excited singlet state (S 1 ) being accessed (ESI 4, Table S2 †). To lend further weight to the identi-cation of the species contributing to the UV/Vis spectra, ab initio explicit solvent theoretical calculations were performed on AQS, AHQS À , and AH 2 QS using ESTEEM [51][52][53] (see Methods section and ESI 6 † for detailed tasks performed). The different nature of the main excitations that contribute to the UV/Vis spectra in AQS and its derivatives, with differing charge-transfer contributions (see ESI 4, Table S1, 2 †), mean that there is quite signicant variation in peak energies between results for different functionals.…”