Computational Reference Data for the Photochemistry of Cyclobutane Pyrimidine Dimers

The cis–syn cyclobutane pyrimidine dimer is one of the major classes of carcinogenic UV-induced DNA photoproducts. In this work, diverse high-level quantum-chemical methods were used to determine the spectroscopic properties of neutral (singlet and triplet) and charged (cation and anion) species of thymine dimers. Maps of potential energy, charge distribution, electron affinity, and ionization potential of the thymidine dimers were computed along the two dimerization coordinates for neutral and charged species, as well as for the singlet excited state. This set of data aims at providing consistent results computed with the same methods as for photodamage and repair. Based on these results, several different photo-, heat-, and charge-induced mechanisms of dimerization and repair are characterized and discussed. Additionally, a new stable dimer with methylmethylidene-hexahydropyrimidine structure was found in the S0 state

Photorelaxation Induced by Water–Chromophore Electron Transfer

Relaxation of photoexcited chromophores is a key factor determining diverse molecular properties, from luminescence to photostability. Radiationless relaxation usually occurs through state intersections caused by distortions in the nuclear geometry of the chromophore. Using excited-state nonadiabatic dynamics simulations based on algebraic diagrammatic construction, it is shown that this is the case of 9H-adenine in water cluster, but not of 7H-adenine in water cluster. 7H-adenine in water cluster relaxes via a state intersection induced by electron transfer from water to the chromophore. This result reveals an unknown reaction pathway, with implications for the assignment of relaxation mechanisms of exciton relaxation in organic electronics. The observation of photorelaxation of 7H-adenine induced by water–chromophore electron transfer is a proof of principle calling for further computational and experimental investigations to determine how common this effect is

Stepwise double excited-state proton transfer is not possible in 7-azaindole dimer

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.MB and NK would like to thank the support from the Deutscher Akademischer Austauschdienst (DAAD) and from the Deutsches Zentrum f¨ur Luft- und Raumfahrt (DLR) through the Thai- German mobility gran

Dynamics simulations of excited-state triple proton transfer in 7-azaindole complexes with water, water–methanol and methanol

Excited-state triple proton transfer (ESTPT) reactions in 7-azaindole (7AI) complexed with two water, with one water and one methanol, and with two methanol molecules were investigated by dynamics simulations in the first excited state computed with the second order algebraic-diagrammatic construction (ADC (2)) method. The results show that photoexcitation may trigger ultrafast an asynchronous concerted proton transfer via two solvent molecules along an intermolecular hydrogen-bonded network. The probability of occurrence of ESTPT ranges from 32% for 7AI(H2O–MeOH) to 64% for 7AI(MeOH)2. The average time for completing the ESTPT varies between 58 and 85 fs depending on the complex. The proton transfer (rather than hydrogen transfer) nature of the reaction was suggested by the nonexistence of crossings between the ππ* and πσ* states

Interfacial States in Donor–Acceptor Organic Heterojunctions: Computational Insights into Thiophene-Oligomer/Fullerene Junctions

Donor–acceptor heterojunctions composed of thiophene oligomers and C60 fullerene were investigated with computational methods. Benchmark calculations were performed with time-dependent density functional theory. The effects of varying the density functional, the number of oligomers, the intermolecular distance, the medium polarization, and the chemical functionalization of the monomers were analyzed. The results are presented in terms of diagrams where the electronic states are classified as locally excited states, charge-transfer states, and delocalized states. The effects of each option for computational simulations of realistic heterojunctions employed in photovoltaic devices are evaluated and discussed

Photo-stability of peptide-bond aggregates: N-methylformamide dimers

E. S.-G acknowledges a Liebig-stipend from the Fonds der Chemischen Industrie. This work was supported by the Cluster of Excellence RESOLV (EXC 1069) funded by the Deutsche Forschungsgemeinschaf

Understanding the Impact of Symmetrical Substitution on the Photodynamics of Sinapate Esters Using Gas-Phase Ultrafast Spectroscopy

Two model biomimetic systems, ethyl sinapate (ES) and its symmetrical analogue, diethyl 2-(4-hydroxy-3,5-dimethoxybenzylidene)malonate (or diethyl sinapate, DES), are stripped to their core fundamentals through gas-phase spectroscopy to understand the underlying photophysics of photothermal materials. Following photoexcitation to the optically bright S1(ππ*) state, DES is found to repopulate the electronic ground state over three orders of magnitude quicker than its non-symmetrical counterpart, ES. Our XMS-CASPT2 calculations shed light on the experimental results, revealing crucial differences in the potential energy surfaces and conical intersection topography between ES and DES. From this work, a peak conical intersection, seen for DES, shows vital importance for the non-radiative ground state recovery of photothermal materials. This fundamental comparative study highlights the potential impact that symmetrical substitution can have on the photodynamics of sinapate esters, providing a blueprint for future advancement in photothermal technology

Photochemistry of methyl hypobromite (CH₃OBr): excited states and photoabsorption spectrum

The singlet and triplet excited states of CH3OBr with excitation energies up to ∼9.5 eV are studied using the multi-reference configuration interaction with singles and doubles method (MRCI-SD) and several single-reference methods, including time-dependent density functional theory (TD-DFT), coupled-cluster (linear-response CC2 and equation-of-motion CCSD and CCSD(T)), and algebraic diagrammatic construction (ADC(2)). Among the single-reference methods, coupled-cluster gives vertical excitation energies and oscillator strengths comparable to the MRCI-SD values for the majority of excited states. The absorption cross section in the gas phase in the region between 2 and 8.5 eV was simulated with CCSD using the nuclear ensemble approach. The computed spectrum predicts two intense absorption bands. The first band, peaked at ∼7.0 eV, is induced by Rydberg excitation. The second band has a strong overlap between a broad σσ* transition and three Rydberg transitions, resulting in two peaks at 7.7 and 7.9 eV. The spectrum also features a low-intensity band peaking at ∼4.6 eV due to nσ* excitation. The intensity of this band is influenced by spin–orbit coupling effects. We analyzed the dissociation pathways along the O–Br and C–O coordinates by computing rigid potential energy curves of the ground and the lowest-lying singlet and triplet excited states, and discussed the possible dissociation products. Due to the specific electronic structure of the excited states, characterized by multireference, double excitations, and Rydberg states occurring in the low-energy region, their correct description along dissociation coordinates is feasible only with MRCI-SD

Theoretical study on excited-state intermolecular proton transfer reactions of 1H-pyrrolo[3,2-h]quinoline with water and methanol

The dynamics of the ultrafast excited-state multiple intermolecular proton transfer (PT) reactions in gas-phase complexes of 1H-pyrrolo[3,2-h]quinoline with water and methanol (PQ(H2O)n and PQ(MeOH)n , where n = 1, 2) is modeled using quantum-chemical simulations. The minimum energy ground-state structures of the complexes are determined. Molecular dynamics simulations in the first excited state are employed to determine reaction mechanisms and the time evolution of the PT processes. Excited-state dynamics results for all complexes reveal synchronous excited-state multiple proton transfer via solvent-assisted mechanisms along an intermolecular hydrogen-bonded network. In particular, excited-state double proton transfer is the most effective, occurring with the highest probability in the PQ(MeOH) cluster. The PT character of the reactions is suggested by nonexistence of crossings between ππ* and πσ* states