Tunneling splitting and decay of metastable states in polyatomic molecules: invariant instanton theory
Literature Information
Gennady Mil’nikov, Hiroki Nakamura
This paper gives an overview of recently developed instanton theory of multidimensional tunneling and demonstrates its applicability to real polyatomic systems. One of the key features of the present formulation is rigorous solution of the multidimensional Hamilton–Jacoby and transport equations which constitutes the basis of the semiclassical theory accurate up to the first order in the Planck constant ℏ. Apart from this fundamental assumption of the semiclassical dynamics the present instanton theory is exact, i.e. it neither involves any further approximation, nor relies on any models. For practical application, the theory is supplemented by numerical methods to construct a multi-dimensional tunneling path (instanton) and to combine the semiclassical theory with high-quality quantum chemical calculations. Emphasis is put on the instanton theory of tunneling splitting in polyatomic molecules. Importance of accurate potential energy surface (PES) information and multidimensional effects is demonstrated by applications to real molecules. The theory of life time of metastable states is also briefly explained.
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DOI: 10.1039/B001766N
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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.














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