| Autor: |
Yu, Hua-Gen, Gonzalez-Lezana, Tomas, Marr, Andrew J., Muckerman, James T., Sears, Trevor J. |
| Předmět: |
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| Zdroj: |
Journal of Chemical Physics; 9/22/2001, Vol. 115 Issue 12, 8 Charts, 8 Graphs |
| Abstrakt: |
New measurements in the A˜ [sup 1]A[sup ″]–X˜ [sup 1]A[sup ′] band system of monobromomethylene (HCBr) at near-infrared wavelengths are reported. Rotationally resolved spectra of HCBr and DCBr for both naturally occurring Br isotopes are analyzed and provide accurate energies for the low-lying bending vibrational levels in both the A˜ and X˜ states. The experimental results are compared to extensive ab initio calculations of these two states and the low-lying a˜ [sup 3]A[sup ″] state. The ab initio T[sub 00] value for the A˜–X˜ system is calculated within 500 cm[sup -1] of the experimental results. For the triplet state, T[sub 00] (α˜–X˜) was calculated to be 1833 cm-1. The measurements of the bending intervals in the X˜ [sup 1]A[sup ′] state suggest that this is about 250 cm-1 too low. With this shift and inclusion of spin–orbit coupling between the a˜ and X˜ states, the calculated bending vibrational levels in the X˜ state reproduce the observations, and the calculations make testable predictions of the position of the triplet and other singlet state vibronic levels. Combining the experimental and computational results, we estimate the triplet, T[sub 00](a˜–X˜), excitation energy to be 2028 cm-1. © 2001 American Institute of Physics. [ABSTRACT FROM AUTHOR] |
| Databáze: |
Complementary Index |
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