Update of the anharmonic force field parameters of the ozone molecule (original) (raw)
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The vibrational and rotational spectra of ozone for the (0, 1, 0) and (0, 2, 0) states
Journal of Molecular Spectroscopy, 1988
The rotational frequencies of the (0, 1, 0) and (0, 2, 0) states and line positions of the v2 and 2~-v2 bands of the normal isotope of ozone have been fitted through J = 65 and K = 2 1 to a three-state Hamiltonian using new measurements in the microwave, far-infrared, and 600-850 cm-' infrared regions. The rms error in the fit is 0.05 MHz for the microwave lines and 0.0006 cm-' for the far-infrared and infrared lines. In addition, intensities of 497 lines of Ye through J = 49 and K = 14 and 45 lines of 2~~-v2 through J = 32 and K = 4 have been fitted to the transition dipole and four interaction terms. Large intensity perturbations are observed due to mixing of the large permanent and vJ dipoles with the smaller vz dipole. o 1988 Academic PIW,, hc. I. INTRODUCTION Ozone has been a subject of many spectroscopic investigations. Most of the relevant microwave references are cited in a recent review (I) and in Ref. (2). Many of the
Chemical Physics Letters, 1991
We. report a benchmark calculation of the structure and harmonic vibrational frequencies of the ozone molecule using the full coupled-cluster single, double, and tripleexcitation model (CCSDT) with a DZP basis set. The resultsoffer a definitive reference for assessing the accuracy of methods which approximate the effects of TX. For the bending and symmetric stretching frequencies, CCSD(T), CCSDT-2, and CCSDT-3 all give results close to CCSDT. For the asymmetric stretching frequency, however, the values predicted by the CCSD(T) and CCSDT-2 models are respeclively about 100 cm-' lower and higher than the CCSDT value, while the CCSDT-3 value exceeds the CCSDT value by 41 cm-'. It is suggested that effects ofconnected quadruple excitations ( T4) and higher cluster operators may have a significant effect on the asymmetric stretching frequency.
International Journal of Quantum Chemistry, 1991
Potential energy surfaces, properties, and spectra of singlet (X ' A ,) and triplet (a3B2) ozone are investigated by means of MCSCF/MCLR analytical response theory calculations. MCSCF analytical gradients and Hessians are used to locate equilibrium and transition-state structures and to obtain associated vibrational and rotational constants, infrared intensities, and dipole moments. By means of MC linear response functions, electronic excitation energies, and oscillator strengths, static and dynamic polarizabilities as well as dispersion (C,) coefficients are obtained. Good agreement is achieved, in some cases within experimental error margins, for properties where experimental data are known. A very low IR intensity for triplet ozone is predicted.
The Journal of Chemical Physics, 2006
To assess the separation of dynamic and nondynamic correlations and orbital choice, we calculate the molecular structure and harmonic vibrational frequencies of ozone with the recently developed tailored coupled cluster singles and doubles method ͑TCCSD͒. We employ the Hartree-Fock and complete active space ͑CAS͒ self-consistent field ͑SCF͒ orbitals to perform TCCSD calculations. When using the Hartree-Fock orbitals, it is difficult to reproduce the experimental vibrational frequency of the asymmetric stretching mode. On the other hand, the TCCSD based on the CASSCF orbitals in a correlation consistent polarized valence triple zeta basis yields excellent results with the two symmetric vibrations differing from the experimental harmonic values by 2 cm −1 and the asymmetric vibration differing by 9 cm −1 .
A systematic ab initio investigation of the open and ring structures of ozone
Chemical Physics Letters, 1998
The energy difference between the open and the ring isomer of ozone as well as the dissociation energy O X, A ™ 3 1 Ž 3 y. Ž 3 .. Ž. O X, S q O P have been determined at the CCSD T , MR-CISD and MR-AQCC levels of theory. Using correlation 2 g Ž. consistent basis sets up to quintuple-zeta quality, the estimated complete basis set limits for CCSD T and MR-AQCC lie within 1 kcalrmol of the experimental value of 26.1 " 0.4 kcalrmol and place the ring isomer by 4.8 and 5.3 kcalrmol, respectively, above the dissociation limit. Zero-point vibrational corrections increase the latter two values by 1.4 kcalrmol.
The Journal of Chemical Physics, 2002
We present an ab initio potential energy surface for the ground electronic state of ozone. It is global, i.e., it covers the three identical C 2v ͑open͒ minima, the D 3h ͑ring͒ minimum, as well as the O(3 P)ϩO 2 (3 ⌺ g Ϫ) dissociation threshold. The electronic structure calculations are performed at the multireference configuration interaction level with complete active space self-consistent-field reference functions and correlation consistent polarized quadruple zeta atomic basis functions. Two of the O-O bond distances, R 1 and R 2 , and the O-O-O bending angle are varied on a regular grid ͑ca. 5000 points with R 1 уR 2). An analytical representation is obtained by a three-dimensional cubic spline. The calculated potential energy surface has a tiny dissociation barrier and a shallow van der Waals minimum in the exit channel. The ring minimum is separated from the three open minima by a high potential barrier and therefore presumably does not influence the low-temperature kinetics. The dissociation energy is reproduced up to 90% of the experimental value. All bound states of nonrotating ozone up to more than 99% of the dissociation energy are calculated using the filter diagonalization technique and employing Jacobi coordinates. The three lowest transition energies for 16 O 3 are 1101.9 cm Ϫ1 ͑1103.14 cm Ϫ1 ͒, 698.5 cm Ϫ1 ͑700.93 cm Ϫ1 ͒, and 1043.9 cm Ϫ1 ͑1042.14 cm Ϫ1 ͒ for the symmetric stretch, the bending, and the antisymmetric stretch modes, respectively; the numbers in parentheses are the experimental values. The root-mean-square error for all measured transition energies for 16 O 3 is only 5 cm Ϫ1. The comparison is equally favorable for all other isotopomers, for which experimental frequencies are available. The assignment is made in terms of normal modes, despite the observation that with increasing energy an increasing number of states acquires local-mode character. At energies close to the threshold a large fraction of states is still unambiguously assignable, particularly those of the overtone progressions. This is in accord with the existence of stable classical periodic orbits up to very high energies.
Chemical Physics Letters, 2004
We have calculated the effect of the symmetric stretching on the dipole polarizability (a ab) of the cyclic form of ozone, O 3 (D 3h). We have used both conventional ab initio and density functional theory methods. All basis sets have been especially designed for polarizability calculations on O 3 (D 3h). At the CCSD(T)/[9s6p5d1f] level of theory the a ab invariants change rapidly around R e = 1.444 Å as aðRÞ=e 2 a 2 0 E À1 h ¼ 16:49 þ 8:68ðR À R e Þ þ 0:38ðR À R e Þ 2 À 2:63ðR À R e Þ 3 þ 0:51ðR À R e Þ 4 ; DaðRÞ=e 2 a 2 0 E À1 h ¼ À6:79 À 7:93ðR À R e Þ þ 0:32ðR À R e Þ 2 þ 2:15ðR À R e Þ 3 : The B3LYP, B3P86 and B3PW91 density functional theory methods agree quite well with the most accurate conventional ab initio values for the mean polarizability at R e but tend to overestimate the magnitude of the anisotropy. The same trend is very much obvious for the derivatives ðd a=dRÞ e and (dDa/R) e .
Chemical Physics Letters, 2000
. We report rovibrational calculations from an empirical potential energy surface PES of the electronic ground state of Ž . ozone, using an Exact Kinetic Energy EKE operator. The PES was optimised using the EKE Hamiltonian and experimental spectroscopic high-resolution data. The RMS deviation of calculations for all experimental band centres directly observed so far in high-resolution spectra is 0.12 cm y1 . The RMS deviation of calculations of rotational energies up to J ( 5 is 0.002 y1 Ž . y1 cm for the 000 level and 0.015 cm for five lowest vibrational states. Both rotational and vibrational calculations are more accurate than presently available EKE-calculations for O . The PES shows a physically meaningful long-range 3 behaviour at the dissociation limit. q
The Journal of Chemical Physics, 2013
An accurate description of the complicated shape of the potential energy surface (PES) and that of the highly excited vibration states is of crucial importance for various unsolved issues in the spectroscopy and dynamics of ozone and remains a challenge for the theory. In this work a new analytical representation is proposed for the PES of the ground electronic state of the ozone molecule in the range covering the main potential well and the transition state towards the dissociation. This model accounts for particular features specific to the ozone PES for large variations of nuclear displacements along the minimum energy path. The impact of the shape of the PES near the transition state (existence of the “reef structure”) on vibration energy levels was studied for the first time. The major purpose of this work was to provide accurate theoretical predictions for ozone vibrational band centres at the energy range near the dissociation threshold, which would be helpful for understandi...
Analysis of the 2ν1+ ν2+ 2ν3Band of Ozone
Journal of Molecular Spectroscopy, 1997
The 2n 1 / n 2 / 2n 3 band of ozone, occurring in the 4780 cm 01 region, has been observed for the first time, using a Fourier transform spectrometer, at 0.008 cm 01 resolution and using a large path length pressure product. Assignments of vibration-rotational transitions have been made up to J Å 48 and K a Å 9. As a few levels with K a Å 1 or 2 are perturbed, it has been necessary to take into account the Coriolis resonance between the and vibrational states. With the effective Hamiltonian explicitly accounting for the interaction between these two states, the fit on 165 energy levels leads to the rms deviation of 1.9 1 10 03 cm 01 , which is near the experimental accuracy. Line intensities of the 2n 1 / n 2 / 2n 3 band have been measured and calculated. The set of spectroscopic parameters for interacting bands, as well as transition moment constants, is given. A complete list of line positions and intensities, with a cutoff of 1 1 10 026 cm 01 /moleculercm 02 at 296 K up to J Å 65 and K a Å 15, has been generated, which leads to the integrated band intensity S v (2n 1 / n 2 / 2n 3 ) Å (5.1 { 2.0) 1 10 023 cm 01 /moleculercm 02 . ᭧ 1997 Academic Press 333