Converged quantum-mechanical calculations of electronic-to-vibrational, rotational energy transfer probabilities in a system with a conical intersection

David W. Schwenke, Steven L Mielke, Gregory J. Tawa, Ronald S. Friedman, Philippe Halvick, Donald G Truhlar

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36 Scopus citations

Abstract

We present quantum-mechanical transition probabilities for the process Na(3p2P) + H2(v0 = 0, j0 = 0,2) → Na(3s2S) + H2(v′, j′) with zero total angular momentum where v0, j0, v′, and j′are initial and final vibrational and rotational quantum numbers. These calculations involve two coupled potential energy surfaces at a total energy of 2.431 eV, and the excited state has energetically accesible geometric configurations with HH internuclear distances 2.7 times larger than the H2 equilibrium internuclear distance - which makes converged quantum-mechanical calculations very difficult. Covergence is demonstrated by obtaining the same results using two entirely different methods - R matrix propagation and the outgoing wave variational principle.

Original languageEnglish (US)
Pages (from-to)565-572
Number of pages8
JournalChemical Physics Letters
Volume203
Issue number5-6
DOIs
StatePublished - Mar 5 1993

Bibliographical note

Funding Information:
We are grateful to Bruce Garrett and Alden Mead for discussions and to David Chatfield for assistance in developing the basis set strategy. This work was supported in part by AHPCRC, MSI, NASA, and NSF.

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