Article
Chemistry, Physical
Isabella C. D. Merritt, Denis Jacquemin, Morgane Vacher
Summary: This study benchmarks the impact of different approximations to the nonadiabatic coupling term on the trajectory surface hopping (TSH) dynamics of isomerization and ring-opening reactions. It is found that the popular local diabatization scheme and a scheme based on biorthonormal wave function overlap in the OpenMOLCAS code can reproduce the dynamics obtained using explicitly calculated nonadiabatic coupling vectors at a reduced cost. However, the other two schemes tested can give different and even incorrect results.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Isabella C. D. Merritt, Denis Jacquemin, Morgane Vacher
Summary: In this study, the impact of various approximation schemes for the coupling term in the trajectory surface hopping (TSH) method is investigated. It is found that two tested schemes, the local diabatization scheme and the biorthonormal wave function overlap scheme, can reproduce the dynamics obtained using explicitly calculated nonadiabatic coupling vectors at a much lower cost. The other two schemes can give different and even incorrect dynamics.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Laura M. Obloy, Patrick Z. El-Khoury, Alexander N. Tarnovsky
Summary: The excited-state dynamics of trans-4,4'-azopyridine in ethanol were investigated using femtosecond transient absorption. Vibrational coherence was observed in both S1 n pi* and S2 pi pi* electronic states. The relaxation pathway showed nonrotational behavior, with population being trapped in planar and shallow minima before decaying into the ground state. Nonrotational relaxation and the formation of hot ground-state species were observed upon excitation of the S2 state. The cis-isomer quantum yield increased with pi pi* excitation, in contrast to trans-azobenzene.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Sapna Ahuja, Sruthy Baburaj, Lakshmy Kannadi Valloli, Sarvar Aminovich Rakhimov, Kavyasree Manal, Aakrati Kushwaha, Steffen Jockusch, Malcolm D. E. Forbes, Jayaraman Sivaguru
Summary: Aryl-maleimides undergo a novel [2+4]-photodimerization instead of the expected [2+2]-photodimerization, and the stereochemistry of the photodimer formed complements the product observed under thermal conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Grant J. Sherborne, Paul Kemmitt, Callum Prentice, Eli Zysman-Colman, Andrew D. Smith, Charlene Fallan
Summary: This study developed a light-mediated cyclisation method for the selective synthesis of tetrahydroquinolines or quinoline derivatives. The method is efficient, atom economical, and tolerant to functional groups, including azaarene-bearing substrates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Christopher B. Larsen, Jason D. Braun, Issiah B. Lozada, Kristjan Kunnus, Elisa Biasin, Charles Kolodziej, Clemens Burda, Amy A. Cordones, Kelly J. Gaffney, David E. Herbert
Summary: Accessing panchromatic absorption and long-lived charge-transfer (CT) excited states is crucial for developing abundant-metal molecular photosensitizers. This study presents an aerobically stable Fe(II) complex with panchromatic absorption and a 3 ns excited-state lifetime, demonstrating the importance of metal-ligand covalency in elongating excited state lifetimes. The findings highlight a novel design principle for extending excited state lifetimes in abundant metal photosensitizers.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Environmental Sciences
Kunni Lin, Deping Hu, Jiawei Peng, Chao Xu, Feng Long Gu, Zhenggang Lan
Summary: Understanding the photochemistry of antibiotic compounds is crucial for addressing environmental pollution concerns. This study utilized a combination of computational methods to investigate the photochemistry of the trans-isomer of nitrofurantoin, providing insights into the photo-induced reaction mechanisms of medium to large-sized drug compounds.
Article
Chemistry, Multidisciplinary
Xuchun Yang, Madushanka Manathunga, Samer Gozem, Jeremie Leonard, Tadeusz Andruniow, Massimo Olivucci
Summary: This study demonstrates the degeneracy between the reactive excited state and a neighboring state in rhodopsin, which causes the splitting of the rhodopsin population into subpopulations after 15 femtoseconds of light absorption. These subpopulations propagate with different velocities and contribute differently to the quantum efficiency. Furthermore, the study reveals that protein electrostatics modulate this splitting and link amino acid sequence variations to quantum efficiency modulation.
Article
Engineering, Environmental
Hongyu Jiang, Fengxia Bao, Jinzhao Wang, Jianhua Chen, Yifan Zhu, Di Huang, Chuncheng Chen, Jincai Zhao
Summary: Photosensitized renoxification of HNO3 produces HONO in a high yield, which is an important source for atmospheric HONO. This study provides evidence of the direct formation of NO2* as a key intermediate during the photosensitizing renoxification of HNO3 using humic acid (HA) as a model environmental photosensitizer. The high HONO yield originates from the heterogeneous reaction of NO2* with co-adsorbed water molecules on HA. This work deepens our understanding of atmospheric HONO formation and the transformation of RNS.
ENVIRONMENTAL SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Physical
Ruibin Liang, Amirhossein Bakhtiiari
Summary: The protein environment plays a crucial role in influencing the photodynamics of photoswitches, which has important implications for the rational design of light-regulated therapeutics.
JOURNAL OF PHYSICAL CHEMISTRY B
(2022)
Article
Chemistry, Physical
Keigo Nagamori, Misato Haze, Hiroyuki Nakata, Oliver Zingsheim, Katsuyoshi Yamasaki, Hiroshi Kohguchi
Summary: The ultraviolet photochemistry of iron pentacarbonyl (Fe(CO)(5)) was investigated using REMPI spectroscopy and ion imaging. The study revealed that the photofragments of CO generated by ultraviolet irradiation of Fe(CO)(5) were in highly vibrationally excited states with v = 11-15, with maximum generation occurring at around 220 nm. The yield spectrum of coordinatively unsaturated intermediates (Fe(CO)(n=1-4)) was found to correlate with that of the high-v CO fragments, suggesting high-v CO generation in the photo-dissociation of Fe(CO). The theoretical calculations of the excited states of FeCO supported the experimental indication of FeCO + converting to Fe + high-v CO.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Biochemistry & Molecular Biology
Melanie Roseau, Laetitia Chausset-Boissarie, Sylvain Gremetz, Philippe M. C. Roth, Mael Penhoat
Summary: This study reports the characterization of commercially available Corning (R) Lab Photo Reactor using azobenzene E <-> Z photoisomerization for actinometry. Compared to previous chemical actinometric protocols, this method based on NMR spectroscopy is rapid, cheap, robust, reproducible, and applicable to the UVA-visible range.
PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES
(2022)
Article
Multidisciplinary Sciences
Simon Axelrod, Eugene Shakhnovich, Rafael Gomez-Bombarelli
Summary: The authors introduce a diabatic neural network to accelerate excited-state, non-adiabatic simulations of azobenzene derivatives and successfully predict quantum yields for unseen species that are correlated with experiment. The model provides a new approach for fast and accurate virtual screening of photoactive compounds.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Mengfei Wang, Kei Murata, Yosuke Koike, Gediminas Jonusauskas, Amaury Furet, Dario M. Bassani, Daisuke Saito, Masako Kato, Yuushi Shimoda, Kiyoshi Miyata, Ken Onda, Kazuyuki Ishii
Summary: A recent study has demonstrated the photo-induced CO-releasing capabilities of the complex Re1Pc, which is composed of a [Re(CO)(3)](+) unit and a phthalocyanine ligand. The complex exhibited efficient spin-orbit coupling and large Franck-Condon factors, resulting in short excited-state lifetimes and ultrafast intersystem crossing. This research provides promising insights into the development of red-light-driven photoCORMs for biomedical applications.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Roseanne J. Sension, Taylor P. McClain, Ryan M. Lamb, Roberto Alonso-Mori, Frederico Alves Lima, Fernando Ardana-Lamas, Mykola Biednov, Matthieu Chollet, Taewon Chung, Aniruddha Deb, Paul A. Dewan Jr, Leland B. Gee, Joel Huang Ze En, Yifeng Jiang, Dmitry Khakhulin, Jianhao Li, Lindsay B. Michocki, Nicholas A. Miller, Florian Otte, Yohei Uemura, Tim B. van Driel, James E. Penner-Hahn
Summary: Femtosecond time-resolved X-ray absorption, X-ray emission, and broadband UV-vis transient absorption were used to investigate the atomic and electronic dynamics of two vitamin B-12 compounds after photoexcitation. Sequential structural evolution and coherent bond elongation were observed, followed by recoil to a relaxed excited state structure. The formation of a metal-centered excited state with a lifetime of 2-5 ps was suggested by time-resolved X-ray emission and optical transient absorption.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)