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Issue 19, 2007
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Torsional anharmonicity in transition state theory calculations

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Abstract

We present a new application for the Torsional Path Integral Monte Carlo (TPIMC) method in which the TPI partition functions are introduced into the calculation of Transition State Theory (TST) rate constants. In this way, an explicit treatment of torsional anharmonicity is included in the TST calculations and the magnitude of these effects can be assessed. The new method is tested on the C2H6 + H hydrogen abstraction reaction and concerted hydrogen transfer in the carbonic acid dimer, for which we have developed torsional potential energy surfaces. For the C2H6 + H reaction the rate constants are halved at room temperature on including a treatment of torsional anharmonicity, while the effects are found to be much smaller for the hydrogen transfer reaction in the carbonic acid dimer.

Graphical abstract: Torsional anharmonicity in transition state theory calculations

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Publication details

The article was received on 22 Jan 2007, accepted on 05 Mar 2007 and first published on 27 Mar 2007


Article type: Paper
DOI: 10.1039/B701014A
Phys. Chem. Chem. Phys., 2007,9, 2397-2405

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    Torsional anharmonicity in transition state theory calculations

    Y. K. Sturdy and D. C. Clary, Phys. Chem. Chem. Phys., 2007, 9, 2397
    DOI: 10.1039/B701014A

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