Instanton theory for the tunneling splitting of low vibrationally excited states.

J Chem Phys

Department of Theoretical Studies, Institute for Molecular Science, Myodaiji, Okazaki 444-8585, Japan.

Published: March 2005

We develop the instanton theory for calculating the tunneling splitting of excited states. For the case of low vibrational quantum states we derive a canonically invariant formula which is applicable to a multidimensional system of arbitrary Riemannian metric. The effect of multidimensionality in relation to the vibrational excitation is explained in terms of the effective frequencies along the instanton trajectory. The theory is demonstrated to work well by taking HO2 molecule as an example.

Download full-text PDF

Source
http://dx.doi.org/10.1063/1.1869989DOI Listing

Publication Analysis

Top Keywords

instanton theory
8
tunneling splitting
8
excited states
8
theory tunneling
4
splitting low
4
low vibrationally
4
vibrationally excited
4
states develop
4
develop instanton
4
theory calculating
4

Similar Publications

The Small- Series in the Zero-Dimensional () Model: Constructive Expansions and Transseries.

Ann Henri Poincare

April 2024

Heidelberg University, Institut für Theoretische Physik, Philosophenweg 19, 69120 Heidelberg, Germany.

We consider the zero-dimensional quartic () vector model and present a complete study of the partition function (, ) and its logarithm, the free energy (, ), seen as functions of the coupling on a Riemann surface. We are, in particular, interested in the study of the transseries expansions of these quantities. The point of this paper is to recover such results using constructive field theory techniques with the aim to use them in the future for a rigorous analysis of resurgence in genuine quantum field theoretical models in higher dimensions.

View Article and Find Full Text PDF

Semiclassical instanton theory for reaction rates at any temperature: How a rigorous real-time derivation solves the crossover temperature problem.

J Chem Phys

November 2024

Simons Center for Computational Physical Chemistry, New York University, New York, New York 10003, USA and Department of Chemistry, New York University, New York, New York 10003, USA.

Instanton theory relates the rate constant for tunneling through a barrier to the periodic classical trajectory on the upturned potential energy surface, whose period is τ = ℏ/(kBT). Unfortunately, the standard theory is only applicable below the "crossover temperature," where the periodic orbit first appears. This paper presents a rigorous semiclassical (ℏ → 0) theory for the rate that is valid at any temperature.

View Article and Find Full Text PDF

Hydrogen-Bonded Complexes of HPN⋅ and HNP⋅ Radicals with Carbon Monoxide.

Angew Chem Int Ed Engl

January 2025

Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, 200433, China.

Phosphorus mononitride (PN) is a carrier of phosphorus in the interstellar medium. As the simplest derivatives of PN, the radical species HPN⋅ and HNP⋅ have remained elusive. Herein, we report the generation, characterization, and photochemistry of HPN⋅ and HNP⋅ in N-matrix at 3 K.

View Article and Find Full Text PDF

Phenyl Radical Activates Molecular Hydrogen Through Protium and Deuterium Tunneling.

Angew Chem Int Ed Engl

December 2024

Institut für Organische Chemie, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, 72076, Tübingen, Germany.

Activating dihydrogen, H, is a challenging endeavor typically achieved using transition metal centers. Pure main-group compounds capable of this are rare and have emerged in recent decades. These systems rely on synergistic donor-acceptor interactions with H's antibonding σ* and bonding σ orbital.

View Article and Find Full Text PDF

Heavy-Atom Tunneling in Ring-Closure Reactions of Beryllium Ozonide Complexes.

J Am Chem Soc

October 2024

Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200438, China.

Quantum mechanical tunneling (QMT) has long been recognized as crucial for understanding chemical reaction mechanisms, particularly in reactions involving light atoms like hydrogen. However, recent findings have expanded this understanding to include heavy-atom tunneling reactions. In this report, we present the observation of two heavy-atom tunneling reactions involving the spontaneous conversions from end-on bonded beryllium ozonide complexes, OBeOOO () and BeOBeOOO (), to their corresponding side-on bonded ozonide isomers, OBe(η-O) () and BeOBe(η-O) (), respectively, in a cryogenic neon matrix.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!