QUANTUM STUDY OF VIBRATIONAL-EXCITATION IN THE 3-DIMENSIONAL COLLISIONS OF CO2 WITH RARE-GAS ATOMS
A combined vibrational close-coupling and rotational infinite order sudden technique is described for calculating vibrational excitation cross sections σνν′, for the three-dimensional collisions of atoms with linear triatomic molecules. The method treats anharmonic, Coriolis, and vibrational angular...
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| Materiálatiipa: | Journal article |
| Giella: | English |
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1981
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| _version_ | 1826266307328212992 |
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| author | Clary, D |
| author_facet | Clary, D |
| author_sort | Clary, D |
| collection | OXFORD |
| description | A combined vibrational close-coupling and rotational infinite order sudden technique is described for calculating vibrational excitation cross sections σνν′, for the three-dimensional collisions of atoms with linear triatomic molecules. The method treats anharmonic, Coriolis, and vibrational angular momentum terms in the molecular Hamiltonian accurately, and is applicable to any realistic potential energy surface expressed in numerical or functional form. Application of the method to X- CO2(ν1ν2λν 3) collisions, where X=He, Ne, or Ar, is described. An accurate anharmonic CO2 potential, expressed in terms of bond and angle displacements, is employed. The X-CO2 interaction potentials are more approximate and are expanded in terms of atom-atom pair potentials. Calculations of σνν′, over a grid of energies sufficient to give rate coefficients kνν′ for transitions between the low-lying states of CO2 for temperatures up to 300 K, have been performed. Propensities for particular collisional excitations involving the symmetric stretch, bending, and asymmetric stretch vibrational modes of CO2 are examined. It is found that the magnitudes of the σνν′ are largely determined by the energy differences between the ν and ν′ levels. For example, excitation of the ground (00 0O) state to the first excited bending state (01 10) is found to be favored. σνν′ for near resonant transitions such as (02 0O)→(02 20) are found to increase with increasing mass of X. Deactivation of the (00 01) state to the (11 10) state is favored over other transitions. The ratios of the deactivation cross section for the level (00 01) to the deactivation cross sections for lower levels such as (01 10) are small, although these ratios do increase with increasing mass of X, in agreement with experimental findings. Comparison of calculated k νν, for deactivation of the (01 10) level, with those obtained in recent photoacoustic experiments is quite encouraging, considering the approximate nature of the X-CO2 interaction potentials used. For X=He and Ne these calculated kνν′ are within a factor of 5 of the experimental results and have the correct temperature dependence, while for X=Ar the calculations are much larger than the experimental results, and the temperature dependence is too shallow. The computer program used in the calculations is automatic and general, and should be applicable to many other atom-linear triatomic molecule collisions. © 1981 American Institute of Physics. |
| first_indexed | 2024-03-06T20:36:54Z |
| format | Journal article |
| id | oxford-uuid:32f21a6b-98ff-4d9f-a7e1-566dfa17d3cd |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T20:36:54Z |
| publishDate | 1981 |
| record_format | dspace |
| spelling | oxford-uuid:32f21a6b-98ff-4d9f-a7e1-566dfa17d3cd2022-03-26T13:17:11ZQUANTUM STUDY OF VIBRATIONAL-EXCITATION IN THE 3-DIMENSIONAL COLLISIONS OF CO2 WITH RARE-GAS ATOMSJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:32f21a6b-98ff-4d9f-a7e1-566dfa17d3cdEnglishSymplectic Elements at Oxford1981Clary, DA combined vibrational close-coupling and rotational infinite order sudden technique is described for calculating vibrational excitation cross sections σνν′, for the three-dimensional collisions of atoms with linear triatomic molecules. The method treats anharmonic, Coriolis, and vibrational angular momentum terms in the molecular Hamiltonian accurately, and is applicable to any realistic potential energy surface expressed in numerical or functional form. Application of the method to X- CO2(ν1ν2λν 3) collisions, where X=He, Ne, or Ar, is described. An accurate anharmonic CO2 potential, expressed in terms of bond and angle displacements, is employed. The X-CO2 interaction potentials are more approximate and are expanded in terms of atom-atom pair potentials. Calculations of σνν′, over a grid of energies sufficient to give rate coefficients kνν′ for transitions between the low-lying states of CO2 for temperatures up to 300 K, have been performed. Propensities for particular collisional excitations involving the symmetric stretch, bending, and asymmetric stretch vibrational modes of CO2 are examined. It is found that the magnitudes of the σνν′ are largely determined by the energy differences between the ν and ν′ levels. For example, excitation of the ground (00 0O) state to the first excited bending state (01 10) is found to be favored. σνν′ for near resonant transitions such as (02 0O)→(02 20) are found to increase with increasing mass of X. Deactivation of the (00 01) state to the (11 10) state is favored over other transitions. The ratios of the deactivation cross section for the level (00 01) to the deactivation cross sections for lower levels such as (01 10) are small, although these ratios do increase with increasing mass of X, in agreement with experimental findings. Comparison of calculated k νν, for deactivation of the (01 10) level, with those obtained in recent photoacoustic experiments is quite encouraging, considering the approximate nature of the X-CO2 interaction potentials used. For X=He and Ne these calculated kνν′ are within a factor of 5 of the experimental results and have the correct temperature dependence, while for X=Ar the calculations are much larger than the experimental results, and the temperature dependence is too shallow. The computer program used in the calculations is automatic and general, and should be applicable to many other atom-linear triatomic molecule collisions. © 1981 American Institute of Physics. |
| spellingShingle | Clary, D QUANTUM STUDY OF VIBRATIONAL-EXCITATION IN THE 3-DIMENSIONAL COLLISIONS OF CO2 WITH RARE-GAS ATOMS |
| title | QUANTUM STUDY OF VIBRATIONAL-EXCITATION IN THE 3-DIMENSIONAL COLLISIONS OF CO2 WITH RARE-GAS ATOMS |
| title_full | QUANTUM STUDY OF VIBRATIONAL-EXCITATION IN THE 3-DIMENSIONAL COLLISIONS OF CO2 WITH RARE-GAS ATOMS |
| title_fullStr | QUANTUM STUDY OF VIBRATIONAL-EXCITATION IN THE 3-DIMENSIONAL COLLISIONS OF CO2 WITH RARE-GAS ATOMS |
| title_full_unstemmed | QUANTUM STUDY OF VIBRATIONAL-EXCITATION IN THE 3-DIMENSIONAL COLLISIONS OF CO2 WITH RARE-GAS ATOMS |
| title_short | QUANTUM STUDY OF VIBRATIONAL-EXCITATION IN THE 3-DIMENSIONAL COLLISIONS OF CO2 WITH RARE-GAS ATOMS |
| title_sort | quantum study of vibrational excitation in the 3 dimensional collisions of co2 with rare gas atoms |
| work_keys_str_mv | AT claryd quantumstudyofvibrationalexcitationinthe3dimensionalcollisionsofco2withraregasatoms |