Overtone Frequencies and Intensities in the Local Mode Picture

Communication: Equivalence between symmetric and antisymmetric stretching modes of NH3 in promoting H + NH3 → H2 + NH2 reaction

“…This observation suggests that the vibrational effect is better analyzed in the local mode regime, in which the stretching vibrations of NH 3 can be approximately considered as linear combinations of the three equivalent N-H bond vibrations. 45 In Table I The hydrogen abstraction reactions in the three systems, i.e., H + H 2 O → H 2 + OH, H + NH 3 → H 2 + NH 2 , and H + CH 4 → H 2 + CH 3 , are benchmark reactions for tetra-, penta-, and hexa-atomic reactions. Thus, it is of great interest to compare the mode specificity in the three reactions, which may bring about in-depth insights into polyatomic reactions.…”

Dissociation and predissociation in the ns 1B1 and np1A2 series of H2O

“…Systems involving two equivalent dissociation channels, such as the ns 1 B 1 series also raise questions about the nature of the dissociation coordinate, because the dissociation to H + OH proceeds along a local mode coordinate, rather than the antisymmetric stretching mode. The difference may be small in practice, if one is concerned only with the predissociation rate, rather than the quantum state dependence of the fragments, but a proper formulation would be in terms of symmetrized local mode wavefunctions [40]. .…”

Vibrational spectra of oxygen and nitrogen-bridged iron octaethylporphyrin dimers by an U(2) algebraic

“…With this definition, due to Child and Halonen [9,10], local-mode molecules are near to the  = 0 limit, normal mode molecules have   1.…”

“…Vibrational assignments of the resonance Raman spectra of various metalloporphyrins have been extensively studied by several groups [5][6][7][8]. Recently, an algebraic approach has been proposed for the study of bio-molecular spectroscopy [9][10]. In the algebraic approach, the vibrational Hamiltonian is expanded in terms of certain operators in Lie algebra; U(4) in the full three-dimensional approach and U (2) in the simpler one-dimensional approach [11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26].…”