Quantum scattering study of collisional energy transfer in He+NO2: The importance of the vibronic mixing

Carlo Petrongolo, George C Schatz

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

We present the results of a quantum scattering study of collisional energy transfer in the title reaction, considering energies up to 14000 cm-1 above the NO2 zero point energy. The collisions are described using the VCC-IOS (vibrational-coupled-channel infinite-order-sudden) quantum scattering method, with two coupled potential surfaces and as many as 329 total states in the basis expansion. The intramolecular potentials describe the X2A′(2A1) and A2A′(2B2) states of NO2, and their coupling through a conical intersection. The intermolecular potential is based on empirical sums of atom-atom potentials. We find that vibronic mixing between the X and A states of NO2 strongly enhances collisional energy transfer and, as a result, there is a noticeable change in the energy transfer efficiency as vibronic energy in NO2 is increased above the threshold for A state excitation. This change in efficiency occurs even if the same intermolecular potential is used for both NO2 electronic states. Many transitions are enhanced because the energy gaps between vibronically mixed and unmixed states are smaller. Energy transfer is also enhanced between states which are both vibronically mixed, whenever a significant component of each state involves the same zeroth order level of the excited electronic state. The calculated results are in good agreement with recent measurements.

Original languageEnglish
Pages (from-to)5672-5678
Number of pages7
JournalJournal of Chemical Physics
Volume112
Issue number13
Publication statusPublished - Apr 1 2000

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Energy transfer
energy transfer
Scattering
Electronic states
scattering
Atoms
Electron transitions
zero point energy
Energy gap
electronics
intersections
atoms
collisions
expansion
thresholds
energy
excitation

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Quantum scattering study of collisional energy transfer in He+NO2 : The importance of the vibronic mixing. / Petrongolo, Carlo; Schatz, George C.

In: Journal of Chemical Physics, Vol. 112, No. 13, 01.04.2000, p. 5672-5678.

Research output: Contribution to journalArticle

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