Photodissociation dynamics of formyl fluoride via the triplet state surface: a direct ab-initio dynamics study

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DOI 10.1039/A901011D
Impact Factor 3.676
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Abstract

Direct ab-initio dynamics calculations have been applied to the photodissociation of the HFCO molecule on the potential energy surface at the triplet state in order to elucidate its reaction mechanism and to determine the energy partitioning in the products. Two reaction channels, HFCO(T1)→H(2S)+FCO(X2A′) and HFCO(T1)→F(2P)+HCO(X2A′) (denoted as channels 1 and 2, respectively) were considered as decay processes of HFCO(T1). Ab-initio molecular orbital calculations showed that the activation barrier for channel 1 is significantly lower than that for channel 2 [96.2 vs. 121.3 kJ mol-1 at the MP4SDQ/6-311++G(2d,p)//MP4SDQ/6-311G(d,p) level of theory]. Direct ab-initio dynamics calculations, carried out at the HF/6-311G(d,p) level, suggested that almost all the available energy is partitioned into the relative translational modes between fragments in channel 1, whereas 60% of the total available energy is partitioned into the internal and rotational modes of the HCO fragment in channel 2. In addition, rotational excitation of the a-axis of the FCO fragment is found in channel 1. The mechanisms of the dissociation reactions are discussed on the basis of the results.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
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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.

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