title: Relating normal vibrational modes to local vibrational modes: benzene and naphthalene.
abstract: Local vibrational modes can be directly derived from normal vibrational modes using the method of Konkoli and Cremer (Int J Quant Chem 67:29, 1998). This implies the calculation of the harmonic force constant matrix F (q) (expressed in internal coordinates q) from the corresponding Cartesian force constant matrix f (x) with the help of the transformation matrix U = WB (†)(BWB (†))(-1) (B: Wilson's B-matrix). It is proven that the local vibrational modes are independent of the choice of the matrix W. However, the choice W = M (-1) (M: mass matrix) has numerical advantages with regard to the choice W = I (I: identity matrix), where the latter is frequently used in spectroscopy. The local vibrational modes can be related to the normal vibrational modes in the form of an adiabatic connection scheme (ACS) after rewriting the Wilson equation with the help of the compliance matrix. The ACSs of benzene and naphthalene based on experimental vibrational frequencies are discussed as nontrivial examples. It is demonstrated that the local-mode stretching force constants provide a quantitative measure for the C-H and C-C bond strength.
authors.affiliation: Department of Chemistry, Southern Methodist University, 3215 Daniel Avenue, Dallas, TX 75275-0314, USA.
authors.forename: Wenli
authors.initials: W
authors.lastname: Zou
authors.forename: Robert
authors.initials: R
authors.lastname: Kalescky
authors.forename: Elfi
authors.initials: E
authors.lastname: Kraka
authors.forename: Dieter
authors.initials: D
authors.lastname: Cremer
mesh_terms: D001554:Benzene / Q000737:chemistry*; D008958:Models, Molecular; D009281:Naphthalenes / Q000737:chemistry*; D011789:Quantum Theory; D013055:Spectrophotometry, Infrared / Q000379:methods; D014732:Vibration
chemical_list: D009281:Naphthalenes; C031721:naphthalene; D001554:Benzene