Fluorophores exhibiting excited-state intramolecular proton transfer (ESIPT) are promising candidates for applications ranging from imaging and probing to laser dyes, optoelectronic devices and molecular logic gates. Recently, ESIPT-active solid-state emitters based on 2′-hydroxychalcone have been synthesized. The compounds are almost non-emissive in solution but emit in the deep red/NIR region when crystalline. Herein, we present a comprehensive theoretical investigation of the gas-phase excited state relaxation pathways in five 2′-hydroxychalcone systems, using a combination of static and non-adiabatic simulations. We identify two competing non-radiative relaxation channels, driven by intramolecular rotation in the enol and keto excited states. Both mechanisms are accessible for the five compounds studied and their relative population depends on the nature of the substituent. The addition of electron-donating substituents greatly increases the propensity of the ESIPT pathway versus rotation in the enol state. The identification of the fundamental relaxation mechanisms is the first step towards understanding the aggregated emission phonomena of these compounds.

The nature of the excited-state double proton transfer in 7-azaindole (7AI) dimer—whether it is stepwise or concerted—has been under a fierce debate for two decades. Based on high-level computational simulations of static and dynamic properties, we show that much of the earlier discussions was induced by inappropriate theoretical modelling, which led to biased conclusions towards one or other mechanism. A proper topographical description of the excited-state potential energy surface of 7AI dimer in the gas phase clearly reveals that the stepwise mechanism is not accessible due to kinetic and thermodynamic reasons. Single proton transfer can occur, but when it does, an energy barrier blocks the transfer of the second proton and the dimer relaxes through internal conversion. Double proton transfer takes place exclusively by an asynchronous concerted mechanism. This case-study illustrates how computational simulations may lead to unphysical interpretation of experimental results.

Bismuth vanadate (BiVO4) is a promising material for photoelectrochemical water splitting and photocatalytic degradation of organic moieties. We evaluate the ionization potentials of the (010) surface termination of BiVO4 using first-principles simulations. The electron removal energy of the pristine termination (7.2 eV) validates recent experimental reports. The effect of water absorption on the ionization potentials is considered using static models as well as structures obtained from molecular dynamics simulations. Owing to the large molecular dipole of H2O, adsorption stabilizes the valence band edge (downward band bending), thereby increasing the ionization potentials. These results provide new understanding to the role of polar layers on complex oxide semiconductors, with importance for the design of efficient photoelectrodes for water splitting.

Graphene oxide quantum dots (GO-QDs) have distinct optoelectronic properties for their application in bio-imaging, drug delivery and photovoltaics. Herein, the effect of OH functionalisation on the optical properties of GO-QDs is studied based on state-of-the-art theoretical simulations. Our calculations predict the effect of OH groups on ionisation potentials, light absorption and emission properties. The mechanism of fluorescence is analysed considering the role of geometry distortion and charge transfer. Moreover, selective functionalisation of positions with large electron–hole separation offers a strategy to tune the optical gap and photoluminescence properties. These results open up new opportunities for the design of GO-QDs for a wide range of applications.

Fluorophores exhibiting excited-state intramolecular proton transfer (ESIPT) are promising candidates for applications ranging from imaging and probing to laser dyes, optoelectronic devices and molecular logic gates. Recently, ESIPT-active solid-state emitters based on 2′-hydroxychalcone have been synthesized. The compounds are almost non-emissive in solution but emit in the deep red/NIR region when crystalline. Herein, we present a comprehensive theoretical investigation of the gas-phase excited state relaxation pathways in five 2′-hydroxychalcone systems, using a combination of static and non-adiabatic simulations. We identify two competing non-radiative relaxation channels, driven by intramolecular rotation in the enol and keto excited states. Both mechanisms are accessible for the five compounds studied and their relative population depends on the nature of the substituent. The addition of electron-donating substituents greatly increases the propensity of the ESIPT pathway versus rotation in the enol state. The identification of the fundamental relaxation mechanisms is the first step towards understanding the aggregated emission phonomena of these compounds.

The nature of the excited-state double proton transfer in 7-azaindole (7AI) dimer—whether it is stepwise or concerted—has been under a fierce debate for two decades. Based on high-level computational simulations of static and dynamic properties, we show that much of the earlier discussions was induced by inappropriate theoretical modelling, which led to biased conclusions towards one or other mechanism. A proper topographical description of the excited-state potential energy surface of 7AI dimer in the gas phase clearly reveals that the stepwise mechanism is not accessible due to kinetic and thermodynamic reasons. Single proton transfer can occur, but when it does, an energy barrier blocks the transfer of the second proton and the dimer relaxes through internal conversion. Double proton transfer takes place exclusively by an asynchronous concerted mechanism. This case-study illustrates how computational simulations may lead to unphysical interpretation of experimental results.