An ab initio direct classical trajectory study of s-tetrazine photodissociation

Literature Information

Publication Date 2002-05-09
DOI 10.1039/B111390A
Impact Factor 3.676
Authors

Xiaosong Li, Smriti Anand, John M. Millam, H. Bernhard Schlegel


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Abstract

The photodissociation of s-tetrazine via a three-body fragmentation channel (C2N2H2 → 2HCN + N2) has been studied by ab initio direct classical trajectory calculations using Hartree–Fock and density functional methods with split valence and polarized basis sets [HF/3-21G, HF/6-31G(d) and B3LYP/6-31G(d)]. The calculated transition state is planar. At our most reliable method (CBS-APNO), the heat of reaction and barrier height are −53.0 kcal mol−1 and 41.1 kcal mol−1, respectively. To simulate the experimental photolysis of s-tetrazine, trajectories were started from a microcanonical ensemble at the transition state with 12 kcal mol−1 excess energy distributed among the vibrational modes and the transition vector. At all levels of theory, the HCN product has a very broad rotational distribution, ranging up to J = 64, and has extensive excitation of the bending vibration. By contrast, N2 is produced with low J and with only a small amount of vibrational excitation in agreement with experiments. In accord with the experiment, the relative translation motion of the products receives about 80–83% of the available energy.

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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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