Towards experimental determination of conical intersection properties: a twin state based comparison with bound excited states

Literature Information

Publication Date 2011-05-27
DOI 10.1039/C1CP20268E
Impact Factor 3.676
Authors

Shmuel Zilberg, Yehuda Haas


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Abstract

The energy and approximate structure of certain S0/S1 conical intersections (CI) are shown computationally to be deducible from those of two bound states: the first triplet (T1), which is iso-energetic with the CI, and the second excited singlet state (S2). This is demonstrated for acepentalene (I) and its perfluoro derivative (II) using the twin state concept for three states systems and based on the fact that the triplet T1 is almost degenerate with the CI. The stable S2 (C3v configuration) state exhibits unusual exaltation of Jahn–Teller active degenerate mode—νJT = 2058 cm−1 (∼500 cm−1 higher than analogous e-mode of the symmetric (C3v) T1 and the dianion I−2 or any C–C vibration of the Jahn–Teller distorted (Cs) ground state minimum). The acepentalene molecule, whose rigid structure and possibility to attain the relatively high symmetry C3v configuration, is a particularly suitable candidate for this purpose.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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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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