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Application of the transfer Hamiltonian formalism to high‐energy model systems
Author(s) -
McClellan Joshua J.,
Hughes Thomas F.,
Bartlett Rodney J.
Publication year - 2005
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.20685
Subject(s) - diatomic molecule , hamiltonian (control theory) , chemistry , nitromethane , trimer , quantum , basis set , coupled cluster , adiabatic process , computational chemistry , quantum mechanics , molecular physics , atomic physics , dimer , chemical physics , physics , molecule , density functional theory , mathematical optimization , mathematics , organic chemistry
We present our recent work toward a transfer Hamiltonian that can more accurately predict the quantum mechanical behavior of nitrogen‐containing energetic materials and their clusters. A new parameterization for a semi‐empirical neglect of diatomic differential overlap Hamiltonian that improves on the standard AM1 parameter set is presented. This new parameterization exactly reproduces the decomposition of nitromethane to CH 3 and NO 2 radicals as predicted with coupled cluster singles and doubles in a triple zeta basis with polarization functions. The transferability of such parameters to small clusters of nitromethane is demonstrated. For nitromethane dimer and trimer, this model transfer Hamiltonian predicts rearrangements similar to previously calculated unimolecular mechanisms. The strained nitromethane trimer studies include the formation of methylnitrite trimer via a concerted rearrangement. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005