Strict Lindemann behaviour because of an activation bottleneck

Vatsya, S. R.; Pritchard, H. O.

doi:10.1016/0301-0104(81)87013-9

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2004

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Cited by 7 publications

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“…The accuracy of the Nesbet algorithm was then tested extensively in a different manner. The matrix A can be transformed into another matrix M having the same set of eigenvalues, but for which there exists an analytical solution 10 for the smallest eigenvalue and eigenvector of [ M + D ]. Over the complete range of pressures, the Nesbet eigenvalue agreed with the analytical solution to the number (7) of significant figures requested.…”

Section: Numerical Resultsmentioning

confidence: 99%

Eigenvalue Methods in Unimolecular Rate Calculations

Pritchard

2004

J. Phys. Chem. A

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When the calculation of a unimolecular reaction rate constant is cast in the form of a master equation eigenvalue problem, the magnitude of that rate is often smaller than the rounding error of the trace of the corresponding reaction matrix. Two available methods to overcome this cancellation problem are examined, and it is shown that one of them, the Nesbet procedure, can fail if the master equation relaxation matrix is improperly normalized, or when some time-saving computational approximations are used.

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Section: Numerical Resultsmentioning

confidence: 99%