Microwave and radiofrequency Stark spectrum of ArHCN: A highly nonrigid molecule

Leopold, K. R.; Fraser, Gerald T.; Lin, Fei; Nelson, David D.; Klemperèr, William

doi:10.1063/1.447476

Cited by 91 publications

(19 citation statements)

References 24 publications

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“…In particular, the value for InNC is abnormally large and in the diatomic approximation implies an InN stretching frequency about one-half the measured value. Since it is the bending modes which seem to be the source of difficulties with the geometry determinations, and the distortion constants of linear molecules normally say little about these, there would appear to be significant coupling between the two modes, along the lines found, for example, for the van der Waals complex Ar-HCN (44). It is perhaps significant that in the ab initio calculations the optimized M-N bond lengths of the isocyanides increased as the MNC angle decreased, while M-C lengths of the cyanides decreased with MCN angle.…”

Section: Discussionmentioning

confidence: 96%

Fourier Transform Microwave Spectroscopy of Cyanides and Isocyanides of Al, Ga, and In

Walker

Evans

Suh

et al. 2001

Journal of Molecular Spectroscopy

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Section: Discussionmentioning

confidence: 96%

Fourier Transform Microwave Spectroscopy of Cyanides and Isocyanides of Al, Ga, and In

Walker

Evans

Suh

et al. 2001

Journal of Molecular Spectroscopy

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“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] Monomers and dimers were investigated both experimentally and theoretically. 3,4,9,[16][17][18][19][20][21][22][23] An ab initio CEPA-I and MP4 potential energy surface for ArHCN was reported by Clary et al 2 and Tao et al, 22 respectively. A host of workers 17,18,21,24,25 experimentally investigated this van der Waals complex, although arriving at no general consensus on the form of its potential energy surface.…”

Section: Introductionmentioning

confidence: 99%

“…3,4,9,[16][17][18][19][20][21][22][23] An ab initio CEPA-I and MP4 potential energy surface for ArHCN was reported by Clary et al 2 and Tao et al, 22 respectively. A host of workers 17,18,21,24,25 experimentally investigated this van der Waals complex, although arriving at no general consensus on the form of its potential energy surface. 22 Gutowsky et al, 3 while investigating experimentally the microwave rotational transitions of Ne-HCN dimer, have also presented a molecularmechanics-for-clusters (MMC) potential energy surface for Rg-HCN dimers with He, Ne, Ar, and Kr as rare gas giving stabilities of 21, 37, 85, and 108 cm -1 , respectively.…”

Section: Introductionmentioning

confidence: 99%

Six-Dimensional Energy-Switching Potential Energy Surface for HeHCN

Ansari

Varandas

2002

J. Phys. Chem. A

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A single-valued six-dimensional (6D) potential energy surface is determined for HeHCN by using the energy switching (ES) method, which utilizes a global double many-body expansion (DMBE) as well as a Legendre polynomial expansion for different energy regimes. The ES potential has a linear van der Waals well of 29.5 cm -1 which is about 4 cm -1 lower than that reported by Drucker et al. [J. Phys. Chem. 1995, 99, 2646 but agrees with one obtained by Atkins and Hutson [ J. Chem. Phys. 1996, 105, 440]. The effect of stretch of CN as well as CH bonds has also been investigated. With stretch, both the DMBE and ES schemes yield slightly deeper wells and steeper repulsion walls in the high energy region. Microwave transitions calculated at 15.9 and 31.3 GHz agree well with experiment and may be assigned to J ) 1 r 0 and J ) 2 r 1, respectively. This frequency is found to decrease with stretch. Finally, this ES potential energy surface has been compared with that of ArHCN reported by one of us [Chem. Phys. Lett. 1998, 297, 458]. Here, the question of transferability of the parameter which scales the Hatree-Fock energy in the rare gas-X (X ) H, C, and N) interaction from ArHCN to HeHCN has also been investigated. The transferability seems to work as it nicely brings out the position of the potential well and the rovibrational levels. The microwave transition, from the ground state (j ) 0, L ) 0, J ) 0) to state (1, 0, 1), found at 98.61 GHz in HeHCN can be compared with one found at about 162.48 GHz in ArHCN, in close agreement with experiment.

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“…The rotational spectrum of the Ar-HCN dimer was first reported by Leopold et al 1 ten years ago. Since then, experimental 2-7 and theoretical [8][9][10] investigations of this interesting system have continued, encouraged no doubt by the unusually strong angular-radial coupling in the intermolecular potential energy surface ͑PES͒.…”

Section: Introductionmentioning

confidence: 88%

Excited ν3 vibrational state of the Ar–HCN and Kr–HCN dimers

Arunan

Emilsson

Gutowsky

1995

The Journal of Chemical Physics

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Prediction of the spectrum for excitation of the van der Waals modes in ArHCN J. Chem. Phys. 93, 7666 (1990); 10.1063/1.459398 8 3Kr nuclear quadrupole coupling, microwave spectrum, and structure of KrHCN Rotational spectra have been observed for an excited vibrational state of the Ar/Kr-HCN dimers in a Balle-Flygare Fourier transform microwave spectrometer with a high temperature nozzle that can be heated to ϳ1300 K. The B, D J , and H J rotational constants found for the excited parent Ar-HCN isotopic species are 1602.475͑3͒ MHz, 164.2͑6͒ kHz, and 309͑5͒ Hz, and for Kr-HCN they are 1176.4493͑3͒ MHz, 41.7͑1͒ kHz, and 56͑1͒ Hz. The 14 N quadrupole interaction a ͑Jϭ1͒ observed in the excited state is Ϫ2.824 ͑Ϫ3.239͒ MHz for Ar͑Kr͒-HCN, slightly smaller than the Ϫ2.844 ͑Ϫ3.268͒ MHz in the ground state. A substitution analysis based on the C and N isotopic species reveals that the C-N distance r s ͑CN͒ increases by ϳ0.013 ͑0.020 Å͒ on excitation of Ar͑Kr͒-HCN. A similar analysis for free DC 15 N gives an increase in r s ͑CN͒ upon 3 excitation of 0.0022 Å. Assignment of the excited state in the dimer as the 3 C-N stretch of the HCN is proposed and discussed.

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Microwave and radiofrequency Stark spectrum of ArHCN: A highly nonrigid molecule

Abstract: Infrared and microwave study of angular-radial coupling effects in Ar-HCN J. Chem. Phys. 91, 3319 (1989); 10.1063/1.456907Fluorescence and dissociative energy transfer in high pressure Ar-HCN mixtures excited by relativistic electrons

Cited by 91 publications

References 24 publications

Fourier Transform Microwave Spectroscopy of Cyanides and Isocyanides of Al, Ga, and In

Fourier Transform Microwave Spectroscopy of Cyanides and Isocyanides of Al, Ga, and In

Six-Dimensional Energy-Switching Potential Energy Surface for HeHCN

Excited ν3 vibrational state of the Ar–HCN and Kr–HCN dimers

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