TITLE

Calculation of argon trimer rovibrational spectrum

AUTHOR(S)
Karlický, František; Lepetit, Bruno; Kalus, René; Gadéa, Florent Xavier
PUB. DATE
May 2007
SOURCE
Journal of Chemical Physics;5/7/2007, Vol. 126 Issue 17, p174305
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
Rovibrational spectra of Ar3 are computed for total angular momenta up to J=6 using row-orthonormal hyperspherical coordinates and an expansion of the wave function on hyperspherical harmonics. The sensitivity of the spectra to the two-body potential and to the three-body corrections is analyzed. First, the best available semiempirical pair potential (HFDID1) is compared with our recent ab initio two-body potential. The ab initio vibrational energies are typically 1–2 cm-1 higher than the semiempirical ones, which is related to the slightly larger dissociation energy of the semiempirical potential. Then, the Axilrod-Teller asymptotic expansion of the three-body correction is compared with our newly developed ab initio three-body potential. The difference is found smaller than 0.3 cm-1. In addition, we define approximate quantum numbers to describe the vibration and rotation of the system. The vibration is represented by a hyper-radial mode and a two-degree-of-freedom hyperangular mode, including a vibrational angular momentum defined in an Eckart frame. The rotation is described by the total angular momentum quantum number, its projection on the axis perpendicular to the molecular plane, and a hyperangular internal momentum quantum number, related to the vibrational angular momentum by a transformation between Eckart and principal-axes-of-inertia frames. These quantum numbers provide a qualitative understanding of the spectra and, in particular, of the impact of the nuclear permutational symmetry of the system (bosonic with zero nuclear spin). Rotational constants are extracted from the spectra and are shown to be accurate only for the ground hyperangular mode.
ACCESSION #
27970949

 

Related Articles

  • Exploring the effect of anharmonicity of molecular vibrations on thermodynamic properties. Njegic, Bosiljka; Gordon, Mark S. // Journal of Chemical Physics;12/14/2006, Vol. 125 Issue 22, p224102 

    Thermodynamic properties of selected small and medium size molecules were calculated using harmonic and anharmonic vibrational frequencies. Harmonic vibrational frequencies were obtained by normal mode analysis, whereas anharmonic ones were calculated using the vibrational self-consistent field...

  • Vibrational overtone spectrum of matrix isolated cis, cis-HOONO. Xu Zhang; Nimlos, Mark R.; Ellison, G. Barney; Varner, Mychel E.; Stanton, John F. // Journal of Chemical Physics;5/7/2007, Vol. 126 Issue 17, p174308 

    Cis, cis-peroxynitrous acid is known to be an intermediate in atmospheric reactions between OH and NO2 as well as HOO and NO. The infrared absorption spectra of matrix-isolated cc-HOONO and cc-DOONO in argon have been observed in the range of 500–8000 cm-1. Besides the seven fundamental...

  • Infrared absorption of gaseous ClCS detected with time-resolved Fourier-transform spectroscopy. Li-Kang Chu; Hui-Ling Han; Yuan-Pern Lee // Journal of Chemical Physics;5/7/2007, Vol. 126 Issue 17, p174310 

    A transient infrared absorption spectrum of gaseous ClCS was detected with a step-scan Fourier-transform spectrometer coupled with a multipass absorption cell. ClCS was produced upon irradiating a flowing mixture of Cl2CS and N2 or CO2 with a KrF excimer laser at 248 nm. A transient band in the...

  • Design of UV laser pulses for the preparation of matrix isolated homonuclear diatomic molecules in selective vibrational superposition states. Korolkov, M. V.; Manz, J. // Journal of Chemical Physics;5/7/2007, Vol. 126 Issue 17, p174306 

    The preparation of matrix isolated homonuclear diatomic molecules in a vibrational superposition state c0·[uppercase_phi_synonym]e=1,v=0+cj·[uppercase_phi_synonym]e=1,v=j, with large (|c0|2≈1) plus small contributions (|cj|2<1) of the ground v=0 and specific v=j low excited...

  • Heterogeneous multicomponent nucleation theorems for the analysis of nanoclusters. Vehkamäki, Hanna; M&;#x00E4;ättänen, Anni; Lauri, Antti; Kulmala, Markku; Winkler, Paul; Vrtala, Aron; Wagner, Paul E. // Journal of Chemical Physics;5/7/2007, Vol. 126 Issue 17, p174707 

    In this paper we present a new form of the nucleation theorems applicable to heterogeneous nucleation. These heterogeneous nucleation theorems allow, for the first time, direct determination of properties of nanoclusters formed on pre-existing particles from measured heterogeneous nucleation...

  • Experimental and Theoretical Studies of the Optical and Electrical Characteristics of a High-Pressure Pulsed Discharge in Argon. Dem’yanov, A. V.; Lo, D. // Plasma Physics Reports;Dec2004, Vol. 30 Issue 12, p1052 

    The optical and electrical characteristics of pulsed discharges in pure Ar at pressures of up to 7 atm, at which the discharge becomes unstable, are studied in a simple experimental device with automatic preionization. The gas temperature in the discharge is estimated from the width of the...

  • Vibrational spectrum of BiH3: Six-dimensional variational calculations on high-level ab initio potential energy surfaces. Yurchenko, Sergei N.; Breidung, Jürgen; Thiel, Walter // Theoretical Chemistry Accounts: Theory, Computation, & Modeling;Oct2005, Vol. 114 Issue 4/5, p333 

    We report a theoretical study of the ground electronic state of BiH3. The potential energy surface (PES) is obtained from coupled cluster CCSD(T) calculations with a large basis set (289 contracted Gaussian functions). The previously available quartic force field (P4) is extended by adding the...

  • Anharmonic vibrational spectroscopy calculations with electronic structure potentials: comparison of MP2 and DFT for organic molecules. Chaban, Galina M.; Gerber, R. Benny // Theoretical Chemistry Accounts: Theory, Computation, & Modeling;Jun2008, Vol. 120 Issue 1-3, p273 

    Density functional theory (DFT) technique is the most commonly used approach when it comes to computation of vibrational spectra of molecular species. In this study, we compare anharmonic spectra of several organic molecules such as allene, propyne, glycine, and imidazole, computed from ab...

  • Calculating molecular vibrational spectra beyond the harmonic approximation. Lin, Ching Yeh; Gilbert, Andrew T. B.; Gill, Peter M. W. // Theoretical Chemistry Accounts: Theory, Computation, & Modeling;Jun2008, Vol. 120 Issue 1-3, p23 

    We present a new approach for calculating anharmonic corrections to vibrational frequency calculations. The vibrational wavefunction is modelled using translated Hermite functions thus allowing anharmonic effects to be incorporated directly into the wavefunction whilst still retaining the...

Share

Read the Article

Courtesy of VIRGINIA BEACH PUBLIC LIBRARY AND SYSTEM

Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics