Infrared spectrum of F/sup -/ /times/ H/sub 2/O

Journal Article · Wed Sep 14 04:00:00 EDT 1988 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00227a008· OSTI ID:6221368

Yates, B F; Schaefer, III, H F; Lee, T J; Rice, J E

Ab initio molecular structure methods have been used in conjunction with high-quality basis sets to determine the geometry and vibrational frequencies of the F/sup -//times/H/sub 2/O system at the self-consistent-field (SCF) and configuration interaction with single and double excitation (CISD) levels of theory. At the CISD level, the largest basis set used was a triple-/zeta/ with two sets of polarization functions and a set of diffuse functions (TZ2P + diff). Anharmonic corrections were determined at the SCF level with a complete quartic force field. In addition, a one-dimensional CISD potential energy surface corresponding to the vibrational mode with the largest predicted infrared intensity (..nu../sub 2/, the asymmetric F-H-O stretch) has been evaluated. Significant deviations from the harmonic approximation are found. At the CISD/TZ2P + diff level of theory, the ..omega../sub 2/ harmonic vibrational frequency is 2670 cm/sup -1/ for F/sup -//times/H/sub 2/O and 1955 cm/sup -1/ for F/sup -//times/D/sub 2/O. With the inclusion of anharmonic effects, the ..nu../sub 2/ fundamental frequencies are predicted to be 1853 cm/sup -1/ (F/sup -//times/H/sub 2/) and 1481 cm/sup -1/ (F/sup -//times/D/sub 2/O). The calculations confirm that the F/sup -//times/H/sub 2/O system is strongly hydrogen bonded and is therefore a likely candidate to be observed via high-resolution infrared spectroscopy. 66 references, 3 figures, 7 tables.

• Research Organization: Univ. of Georgia, Athens (USA)
• DOE Contract Number: FG09-87ER13811
• OSTI ID: 6221368
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 110:19; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ANIONS
CHARGED PARTICLES
DATA
ELECTRONIC STRUCTURE
EXPERIMENTAL DATA
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
HYDRATES
INFORMATION
INFRARED SPECTRA
IONS
NUMERICAL DATA
SPECTRA