Rotational predissociation, vibrational mixing, and van der Waals intermolecular potentials of NeDF

The near‐infrared spectrum of NeDF formed in a slit free jet expansion is recorded with a high resolution, tunable laser spectrometer. Four bands, consisting of the DF stretching fundamental and three internal rotation and van der Waals stretch combination bands, are observed and analyzed for both the 20Ne and 22Ne isotopomers. All three combination bands reveal a sudden onset of rotational predissociation at modest J, which is modeled with effective one‐dimensional potentials to determine the binding energy D0=34.7±0.8 cm−1 for 20NeDF (v=0) and D0=35.1±0.8 cm−1 for 20 NeDF (v=1). The experimental results are compared with predictions of a recently published ab initio anisotropic potential surface, and an improved potential is developed and tested. This refined potential has an absolute minimum of −86 cm−1 in the linear Ne–D–F geometry, a secondary minimum at −55 cm−1 in the inverted linear Ne–F–D geometry, and an intervening saddle point at −39 cm−1 near the perpendicular geometry. The lowest bound state...

[1]  G. Herzberg,et al.  Molecular Spectra and Molecular Structure , 1992 .

[2]  D. Nesbitt,et al.  Mode specific internal and direct rotational predissociation in HeHF, HeDF, and HeHCl: van der Waals complexes in the weak binding limit , 1990 .

[3]  G. T. Fraser,et al.  Microwave spectrum and electric dipole moment of NeHF , 1990 .

[4]  J. Hutson.  Anisotropic intermolecular potentials. III. Rare‐gas–hydrogen bromide systems , 1989 .

[5]  D. Nesbitt,et al.  Intramolecular dynamics of van der Waals molecules: An extended infrared study of ArHF , 1989 .

[6]  D. Clary,et al.  Slit jet infrared spectroscopy of NeHF complexes: Internal rotor and J‐dependent predissociation dynamics , 1989 .

[7]  D. Clary,et al.  Weakly bound NeHF , 1989 .

[8]  D. Clary,et al.  Calculation of vibration–rotation spectra for rare gas–HCl complexes , 1989 .

[9]  Jeremy M. Hutson,et al.  The intermolecular potential of Ne–HCl: Determination from high‐resolution spectroscopy , 1988 .

[10]  R. C. Cohen,et al.  Tunable far infrared laser spectroscopy of van der Waals bonds: Extended measurements on the lowest Σ bend of ArHCl , 1988 .

[11]  D. Nesbitt,et al.  The near-infrared spectrum of NeHCl , 1988 .

[12]  D. Nesbitt,et al.  Infrared-active combination bands in ArHCl , 1988 .

[13]  D. Nesbitt,et al.  Slit pulsed valve for generation of long‐path‐length supersonic expansions , 1987 .

[14]  D. Nesbitt,et al.  High sensitivity, high‐resolution IR laser spectroscopy in slit supersonic jets: Application to N2HF ν1 and ν5+ν1−ν5 , 1987 .

[15]  K. Jucks,et al.  The argon–hydrogen fluoride binary complex: An example of a long lived metastable system , 1986 .

[16]  G. T. Fraser,et al.  van der Waals potentials from the infrared spectra of rare gas–HF complexes , 1986 .

[17]  R. Saykally,et al.  Vibrational spectroscopy of van der Waals bonds: Measurement of the perpendicular bend of ArHCl by intracavity far infrared laser spectroscopy of a supersonic jet , 1986 .

[18]  A. Pine,et al.  Rotational predissociation and libration in the infrared spectrum of ArHCl , 1985 .

[19]  A. Charo,et al.  Characterization of the lowest‐lying Π bending state of Ar–HCl by far infrared laser–Stark spectroscopy and molecular beam electric resonance , 1985 .

[20]  G. Gallup,et al.  A variation‐perturbation method for atomic and molecular interactions. II. The interaction potential and van der Waals molecule for Ne–HF , 1985 .

[21]  G. Delgado-barrio,et al.  Rotational predissociation in polar systems. The He - HF example , 1984 .

[22]  J. Hutson.  Vibrational predissociation and infrared spectrum of the Ar–HCl van der Waals molecule , 1984 .

[23]  C. J. Ashton,et al.  Rotational predissociation of the Ar⋅HCl van der Waals complex: Close‐coupled scattering calculations , 1983 .

[24]  J. Hutson,et al.  Anisotropic intermolecular forces: II. Rare gas-hydrogen fluoride systems , 1982 .

[25]  M. Waldman,et al.  Internal dynamics of van der Waals complexes. I. Born–Oppenheimer separation of radial and angular motion , 1977 .

[26]  S. A. Lee,et al.  Interferometric real‐time display of cw dye laser wavelength with sub‐Doppler accuracy , 1976 .

[27]  R. L. Roy,et al.  Intermolecular potentials and isotope effects for molecular hydrogen–inert gas complexes , 1975 .

[28]  A. Pine.  Doppler-limited molecular spectroscopy by difference-frequency mixing* , 1974 .

[29]  F. Stillinger,et al.  Hydrogen bonding between neon and hydrogen fluoride , 1974 .

[30]  M. L. Martin,et al.  Infrared Spectra of Highly Compressed Gas Mixtures of the Type HCl+X. A Theoretical Study , 1965 .

[31]  A. Weber.  Structure and Dynamics of Weakly Bound Molecular Complexes , 1987 .

[32]  C. F. Curtiss,et al.  Molecular Theory Of Gases And Liquids , 1954 .