Predicting PH vibrations of gas phase molecules and surface-adsorbed species using bond length-frequency correlations
✍ Scribed by Ujjal Das; Krishnan Raghavachari
- Publisher
- John Wiley and Sons
- Year
- 2009
- Tongue
- English
- Weight
- 209 KB
- Volume
- 30
- Category
- Article
- ISSN
- 0192-8651
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✦ Synopsis
Abstract
The high frequency XH (e.g., X = C, Si) stretching modes in small molecules are only slightly perturbed by other vibrational modes present in the system. The isolated frequencies, in these cases, exhibit a linear relationship with the corresponding bond lengths. Here, we study such a bond length‐frequency correlation in the case of PH stretching vibrations for molecules in the gas phase as well as for surface‐adsorbed species. Although a high degree of linear correlation is found, there is a small dependence on the local coordination around P, leading to significant deviations in some cases. By a careful analysis, we show that such correlations can be used to predict new surface frequencies without computing the Hessian matrix explicitly. © 2008 Wiley Periodicals, Inc. J Comput Chem, 2009