Accounting for the dependence of P(E′,E) on the maximum impact parameter in classical trajectory calculations: Application to the H2O–H2O collisional relaxation

Bustos-Marún, Raúl A.; Coronado, Eduardo A.; Ferrero, Juan C.

doi:doi:10.1063/1.2794760

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An eight-degree-of-freedom, time-dependent quantum dynamics study for the H₂+C₂H reaction on a new modified potential energy surface

An eight-dimensional time-dependent quantum dynamics wave packet approach is performed for the study of the H2+C2H→H+C2H2 reaction system on a new modified potential energy surface (PES) [ L.-P. Ju et al., Chem. Phys. Lett. 409, 249 (2005) ]. This new potential energy surface is obtained by modifying Wang and Bowman’s old PES [ J. Chem. Phys. 101, 8646 (1994) ] based on the new ab initio calculation. This new modified PES has a much lower transition state barrier height at 2.29 kcal/mol than Wa...

Observation of three weakly bound valence states of I₂

Structured emission in the gas phase to two weakly bound valence states that correlate with the third dissociation limit, I*(2P1/2)+I*(2P1/2), designated as (bb), from two third tier ion-pair states of I2 correlating with I−(1S0)+I+(1D2), the 1g(1D2), and F′0u+(1D2) states, has been observed for the first time. The 1u(bb) state is shown to be bound by 377±2 cm−1 and molecular constants have been determined. Vibrational structure in the 0g+(bb) state could not be resolved but the spectrum is con...

In this work we report a novel methodology that is able to predict how energy transfer transition probability density functions [P(E′,E)] change with the maximum impact parameter (b_max) used in trajectory calculations (TC’s). The method assumes that P(E′,E) can be described by a sum of exponential functions and that all the trajectories with an initial impact parameter beyond a certain critical value will contribute only to the elastic peak [P(E′,E) for E′ = E]. This approach is applied to H₂O–H₂O collisions at different initial vibrational energies of the excited molecules and temperatures of bath gas. The results show that it is possible to reproduce with high accuracy the whole P(E′,E) obtained from a given b_max, using the results of TC’s performed at another b_max. The new methodology also leads us to propose a new criterion to choose the value of b_max.

Article Outline

INTRODUCTION
THEORY
APPLICATION TO THE SELF COLLISIONAL RELAXATION OF H₂O
1. Trajectory calculations
2. Results
CONCLUSIONS

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KEYWORDS and PACS

Keywords

excited states, molecule-molecule collisions, probability, vibrational states, water

PACS

33.15.Mt

Rotation, vibration, and vibration-rotation constants
34.10.+x

General theories and models of atomic and molecular collisions and interactions (including statistical theories, transition state, stochastic and trajectory models, etc.)
34.50.-s

Scattering of atoms and molecules
33.20.Tp

Vibrational analysis

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http://link.aip.org/link/doi/10.1063/1.2794760

PUBLICATION DATA

ISSN:

0021-9606 (print)

1089-7690 (online)

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$abstract.society.value is a Member of CrossRef

American Institute of Physics

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