Local mode analysis of the CD stretching fundamental and overtone spectra of deuterated dihalomethanes

Journal Article · Thu Mar 13 04:00:00 EST 1986 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100278a025· OSTI ID:5827084

Ahmed, M K; Henry, B R

The overtone spectra of CD/sub 2/Z/sub 2/ (Z = Cl, Br, or I) molecules in the liquid phase are measured in the region of the CD stretching local mode overtones corresponding to ..delta.. nu/sub CD/ = 2-5 (CD/sub 2/Cl/sub 2/ and CD/sub 2/Br/sub 2/) and ..delta.. nu/sub CD/ = 2-4 (CD/sub 2/I/sub 2/). These spectra, and those of the previously reported fundamentals, are analyzed in terms of the local mode model. At a given quantum number nu = nu/sub 1/ + nu/sub 2/, the vibrational states corresponding to CD stretching are taken as symmetry-adapted states of the type absolute value nu/sub 1/, nu/sub 2/> +/-= (1/2/sup 1/2/(absolute value nu /sub 1/nu/sub 2/> +/- nu/sub 2/,nu/sub 1/>), where absolute value nu/sub 1/,nu/sub 2/> = absolute value nu/sub 1/>absolute value nu/sub 2/> is the Morse oscillator product function of the two bond wave functions. Intramanifold coupling between the symmetrized states is determined from a harmonic coupling model, and intermanifold coupling is neglected. The agreement between the calculated and observed spectra is found to be good. A comparison of the spectra of the CD/sub 2/Z/sub 2/ and CH/sub 2/Z/sub 2/ molecules reveals the manifestations of increased coupling between the CD bonds. 19 references, 4 figures, 3 tables.

• Research Organization: Univ. of Manitoba, Winnipeg
• OSTI ID: 5827084
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 90:6; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALKANES
ANIONS
BROMIDES
BROMINE COMPOUNDS
CHARGED PARTICLES
CHLORIDES
CHLORINE COMPOUNDS
DATA
DEUTERIUM COMPOUNDS
ENERGY LEVELS
EXCITED STATES
EXPERIMENTAL DATA
FUNCTIONS
HALIDES
HALOGEN COMPOUNDS
HYDROCARBONS
HYDROGEN COMPOUNDS
INFORMATION
IODIDES
IODINE COMPOUNDS
IONS
ISOTOPE EFFECTS
METHANE
NORMAL-MODE ANALYSIS
NUMERICAL DATA
ORGANIC COMPOUNDS
VIBRATIONAL STATES
WAVE FUNCTIONS