Direct photoisomerization of CH2I2vs. CHBr3 in the gas phase: a joint 50 fs experimental and multireference resonance-theoretical study
Literature Information
Veniamin A. Borin, Sergey M. Matveev, Darya S. Budkina, Patrick Z. El-Khoury, Alexander N. Tarnovsky
Femtosecond transient absorption measurements powered by 40 fs laser pulses reveal that ultrafast isomerization takes place upon S1 excitation of both CH2I2 and CHBr3 in the gas phase. The photochemical conversion process is direct and intramolecular, i.e., it proceeds without caging media that have long been implicated in the photo-induced isomerization of polyhalogenated alkanes in condensed phases. Using multistate complete active space second order perturbation theory (MS-CASPT2) calculations, we investigate the structure of the photochemical reaction paths connecting the photoexcited species to their corresponding isomeric forms. Unconstrained minimum energy paths computed starting from the S1 Franck–Condon points lead to S1/S0 conical intersections, which directly connect the parent CHBr3 and CH2I2 molecules to their isomeric forms. Changes in the chemical bonding picture along the S1/S0 isomerization reaction path are described using multireference average coupled pair functional (MRACPF) calculations in conjunction with natural resonance theory (NRT) analysis. These calculations reveal a complex interplay between covalent, radical, ylidic, and ion-pair dominant resonance structures throughout the nonadiabatic photochemical isomerization processes described in this work.
Recommended Journals

Russian Journal of General Chemistry

Current Opinion in Colloid & Interface Science

Organic Process Research & Development

Chemical Communications

Russian Journal of Bioorganic Chemistry

Russian Journal of Coordination Chemistry

Russian Journal of Applied Chemistry

Nature Medicine

Russian Journal of Organic Chemistry

Saudi Pharmaceutical Journal
Related Literature
The Crystal-T algorithm: a new approach to calculate the SLE of lipidic mixtures presenting solid solutions
Guilherme J. Maximo, Mariana C. Costa, Antonio J. A. Meirelles
DOI: 10.1039/C4CP01529K
Tunability of hybridized plasmonic waveguide mediated by surface plasmon polaritons
Ming-Ming Jiang, Chong-Xin Shan, De-Zhen Shen
DOI: 10.1039/C4CP01437E
Molecular simulation of gas adsorption and diffusion in a breathing MOF using a rigid force field
E. García-Pérez, P. Serra-Crespo, S. Hamad, F. Kapteijn, J. Gascon
DOI: 10.1039/C3CP55416C
Microsolvation of 2-azetidinone: a model for the peptide group–water interactions
Juan C. López, Raquel Sánchez, Susana Blanco, José L. Alonso
DOI: 10.1039/C4CP04577G
The mechanism of the Pd-catalyzed formation of coumarins: a theoretical study
S. Nedd
DOI: 10.1039/C4CP03418J
Yolk–shell structured Gd2O3:Eu3+ phosphor prepared by spray pyrolysis: the effect of preparation conditions on microstructure and luminescence properties
Jung Sang Cho, Kyeong Youl Jung, Yun Chan Kang
DOI: 10.1039/C4CP03477E
The substituent effect on the MLCT excited state dynamics of Cu(i) complexes studied by femtosecond time-resolved absorption and observation of coherent nuclear wavepacket motion
Linqiang Hua, Munetaka Iwamura
DOI: 10.1039/C4CP03843F
Alkali metal cation binding affinities of cytosine in the gas phase: revisited
Bo Yang, M. T. Rodgers
DOI: 10.1039/C4CP01128G
From zeolite nets to sp3 carbon allotropes: a topology-based multiscale theoretical study
Igor A. Baburin, Vladimir A. Saleev, Alexandra V. Shipilova
DOI: 10.1039/C4CP04569F
You might also like
Is 2-(2-chloroacetamido)-3-phenylpropanoic acid (CAS: 7765-11-9) safe?
2-(2-Chloroacetamido)-3-phenylpropanoic acid (CAS: 7765-11-9) is generally consi...
Is 2-(Benzyloxy)-5-bromobenzoic acid (CAS: 62176-31-2) safe?
2-(Benzyloxy)-5-bromobenzoic acid can be handled safely if appropriate precautio...
What is (4-Methyl-1,2,5-oxadiazol-3-yl)methanamine hydrochloride (CAS: 1159825-48-5)?
(4-Methyl-1,2,5-oxadiazol-3-yl)methanamine hydrochloride is a chemical compound ...
What is 2-(5-Hexylthiophen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (CAS: 917985-54-7)?
2-(5-Hexylthiophen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (CAS: 917985-54...
Are there alternatives to 4-(8-Methyl-9H-1,3-dioxolo[4,5-h][2,3]benzodiazepin-5-yl)benzenamine (CAS: 102771-26-6) in synthesis?
While 4-(8-Methyl-9H-1,3-dioxolo[4,5-h][2,3]benzodiazepin-5-yl)benzenamine (CAS:...
What is the market or research trend for tert-butyl 3-hydroxy-4,5,7,8-tetrahydro-2H-pyrazolo[3,4-d]azepine-6-carboxylate (CAS: 851376-80-2)?
The market for tert-butyl 3-hydroxy-4,5,7,8-tetrahydro-2H-pyrazolo[3,4-d]azepine...
How should waste containing 3,5-Diamino-1H-pyrazole-4-carbonitrile (CAS: 6844-58-2) be handled?
Waste containing 3,5-Diamino-1H-pyrazole-4-carbonitrile (CAS: 6844-58-2) should ...
How is (6-Fluoro-3-pyridinyl)boronic acid (CAS: 351019-18-6) typically synthesized?
(6-Fluoro-3-pyridinyl)boronic acid can be synthesized through the reaction of 6-...
What industries use Dibenzyl carbonimidoylbiscarbamate (CAS: 10065-79-9)?
Dibenzyl carbonimidoylbiscarbamate (CAS: 10065-79-9) finds applications in vario...
What is the market or research trend for (beta,beta,2,3,4,5,6-~2~H_7_)Phenylalanine (CAS: 74228-83-4)?
The market for (beta,beta,2,3,4,5,6-~2~H_7_)Phenylalanine (CAS: 74228-83-4) is g...
Source Journal
Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.




