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Predicting PH vibrations of gas phase molecules and surface‐adsorbed species using bond length‐frequency correlations
Author(s) -
Das Ujjal,
Raghavachari Krishnan
Publication year - 2009
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.21187
Subject(s) - hessian matrix , bond length , molecule , vibration , adsorption , chemistry , gas phase , molecular vibration , phase (matter) , surface (topology) , molecular physics , computational chemistry , chemical physics , thermodynamics , physics , mathematics , quantum mechanics , geometry , organic chemistry
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