F And G Intensity Sum Rule Applications: The Chxd4-x Molecules

Numerical analyses based on the F and G intensity sum rules show that recently published experimental values for the fundamental vibrational intensities of CH4, CH3D, CH2D2, CHD3, and CD4 are internally consistent within experimental errors. Effective charge values for the carbon and hydrogen atoms obtained using the intensity sums for all these isotopically related molecules are almost in exact agreement with reported values obtained from the polar tensors of CH4 and CD4. The G sum rule allows a determination of the signs of the dipole moment derivatives using the fundamental intensity sum for CH4 (or CD4) and the polar tensor values for CD4 (or CH4). © 1978 American Institute of Physics.6994147414

Experimental Determination Of Relative Signs Of Dipole Moment Derivatives: Hcn And Dcn

An alternative numerical analysis for the experimental determination of the relative signs of the dipole moment derivatives with respect to the normal coordinates is presented. Use is made of the polar tensor and effective charge equations and the G-intensity sum rule of Crawford. The relative signs are determined by sufficiently accurate individual infrared fundamental intensities of one molecule and only the sum of these intensities for an isotopically related molecule. The intensity data of HCN and DCN are used to illustrate the procedure. The as yet unreported values of the atomic polar tensors and effective charges of these molecules are also reported. © 1978 American Institute of Physics.68384785