Back to Search
Start Over
Carbon dioxide photolysis from 150 to 210 nm: Singlet and triplet channel dynamics, UV-spectrum, and isotope effects.
- Source :
- Proceedings of the National Academy of Sciences of the United States of America; 10/29/2013, Vol. 110 Issue 44, p17691-17696, 6p
- Publication Year :
- 2013
-
Abstract
- We present a first principles study of the carbon dioxide (CO<subscript>2</subscript>) photodissociation process in the 150- to 210-nm wavelength range, with emphasis on photolysis below the carbon monoxide + O(<superscript>1</superscript>D) singlet channel threshold at ~167 nm. The calculations reproduce experimental absorption cross-sections at a resolution of ~0.5 nm without scaling the intensity. The observed structure in the 150- to 210-nm range is caused by excitation of bending motion supported by the deep wells at bent geometries in the 2<superscript>1</superscript>A' and 1<superscript>1</superscript>A“ potential energy surfaces. Predissociation below the singlet channel threshold occurs via spin-orbit coupling to nearby repulsive triplet states. Carbon monoxide vibrational and rotational state distributions in the singlet channel as well as the triplet channel for excitation at 157 nm satisfactorily reproduce experimental data. The cross-sections of individual CO<subscript>2</subscript> isotopologues (<superscript>12</superscript><superscript>C16</superscript>O<subscript>2</subscript>, <superscript>12</superscript>C<superscript>17</superscript>O<superscript>16</superscript>O, <superscript>12</superscript>C<superscript>18</superscript>O<superscript>16</superscript>O, <superscript>13</superscript>C<superscript>16</superscript>O<subscript>2</subscript>, and <superscript>13</superscript>C<superscript>18</superscript>O<superscript>16</superscript>O) are calculated, demonstrating that strong isotopic fractionation will occur as a function of wavelength. The calculations provide accurate, detailed insight into CO<subscript>2</subscript> photoabsorption and dissociation dynamics, and greatly extend knowledge of the temperature dependence of the cross-section to cover the range from 0 to 400 K that is useful for calculations of propagation of stellar light in planetary atmospheres. The model is also relevant for the interpretation of laboratory experiments on mass-independent isotopic fractionation. Finally, the model shows that the mass-independent fractionation observed in a series of Hg lamp experiments is not a result of hyperfine interactions making predissociation of <superscript>17</superscript>O containing CO<subscript>2</subscript> more efficient. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 00278424
- Volume :
- 110
- Issue :
- 44
- Database :
- Complementary Index
- Journal :
- Proceedings of the National Academy of Sciences of the United States of America
- Publication Type :
- Academic Journal
- Accession number :
- 91760251
- Full Text :
- https://doi.org/10.1073/pnas.1213083110