The pure rotational spectrum of the actinide-containing compound thorium monoxide

Dewberry, Christopher T.; Etchison, Kerry C.; Cooke, Stephen A.

doi:10.1039/b709343h

Cited by 38 publications

(30 citation statements)

References 17 publications

(32 reference statements)

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“…The matrix-isolation IR data show the following matrix shifts: with respect to Ne there is a red-shift of 28 cm À1 in Ar, 40 cm À1 in Kr, and 51 cm À1 in Xe. Wang et al 19 carried out DFT calculations on the UO 2 þ , UO 2 (Ne) 6 þ , UO 2 (Ar) 5 þ , UO 2 (Kr) 5 þ , and UO 2 (Xe) 5 þ species to model the effect of matrix on the vibrational frequencies. From their data, we derived somewhat smaller matrix shifts for ν as than found experimentally, viz., 27, 32, and 42 cm À1 in Ar, Kr, and Xe matrices, respectively, with respect to the frequency in the Ne matrix.…”

Section: Computational Detailsmentioning

confidence: 99%

Computed Vibrational Frequencies of Actinide Oxides AnO^0/+/2+ and AnO₂^0/+/2+ (An = Th, Pa, U, Np, Pu, Am, Cm)

Kovács

Konings

2011

J. Phys. Chem. A

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The vibrational frequencies of the actinide oxides AnO and AnO(2) (An = Th, Pa, U, Np, Pu, Am, Cm) and of their mono- and dications have been calculated using advanced quantum chemical techniques. The stretching fundamental frequencies of the monoxides have been determined by fitting the potential function to single-point energies obtained by relativistic CASPT2 calculations along the stretching coordinate and on this basis solving numerically the ro-vibrational Schrödinger equation. To obtain reliable fundamental frequencies of the dioxides, we developed an empirical approach. In this approach the harmonic vibrational frequencies of the AnO(2)(0/+/2+) species were calculated using eight different exchange-correlation DFT functionals. On the basis of the good correlation found between the vibrational frequencies and computed bond distances, the final frequency values were derived for the CASPT2 reference bond distances from linear regression equations fitted to the DFT data of each species. As a test, the approach provided excellent agreement with accurate experimental data of ThO, ThO(+), UO, and UO(+). The joint analysis of literature experimental and our computed data facilitated the prediction of reliable gas-phase molecular properties for some oxides. They include the stretching frequencies of PuO, ThO(2), UO(2), and UO(2)(+) and the bond distance of PuO (1.818 Å, being likely within 0.002 Å of the real value). Also the derived equilibrium bond distances of ThO(2), UO(2), and UO(2)(+) (1.896, 1.790, and 1.758 Å, respectively) should approximate closely the (yet unknown) experimental values. On the basis of the present results, we suggest that the ground electronic state of PuO(2) in Ar and Kr matrices is probably different from that in the gaseous phase, similarly to UO(2) observed previously.

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Section: Computational Detailsmentioning

confidence: 99%

Computed Vibrational Frequencies of Actinide Oxides AnO^0/+/2+ and AnO₂^0/+/2+ (An = Th, Pa, U, Np, Pu, Am, Cm)

Kovács

Konings

2011

J. Phys. Chem. A

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“…In addition to obtaining very accurate molecular constants, these measurements demonstrate that the sensitive and versatile PPMODR technique can be readily applied to heavy element compounds over a wide frequency range. Prior to the results reported here, the only actinide containing molecules for which rotational transitions had been reported were ThO [5][6][7] and UO [8].…”

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confidence: 94%

The pure rotational spectrum of thorium monosulfide, ThS

Steimle

Zhang

2015

Chemical Physics Letters

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Please cite this article as: T.C. Steimle, R. Zhang, M.C. Heaven, The pure rotational spectrum of thorium monosulfide, ThS., Chem. Phys. Lett. (2015), http://dx.A c c e p t e d M a n u s c r i p t Highlights  First rotational spectrum of a ThXmolecule , where X is not O.  Accurate determination of bond length.  DFT prediction surprisingly good given the multi configurational nature.  Demonstration of the power/versatility of the PPMODR method. AbstractThe separated field, pump/probe microwave optical double resonance technique was used to study the pure rotational transitions of Th 32 S X 1  + . This is the first example of a microwave study of an actinide compound that is not an oxide. Eight rotational lines of ThS were observed, from which the rotational constants B=3275.050330.00041 and D=0.00066990.0000012 MHz were derived. Favorable comparisons with theoretical predictions support the assumption that computationally inexpensive Density Functional Theory methods can provide reliable predictions for ground states of actinide-containing molecules.

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“…The determined parameters are (in wavenumbers, cm 1 + (v = 0) state (=1.842 17 Å) is identical to that determined from the pure rotational spectrum 7 and slightly smaller than the recent ab initio prediction of 1.846 Å. 10 The R value for E(0…”

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confidence: 98%

“…While there have been several spectroscopic studies of the ground and low-lying electronic states, [3][4][5][6][7][8] In the present study we have measured the Stark effect for numerous branch features of the E(0 We also analyze the field-free spectrum to derive the bond distances for the E(0…”

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Communication: The permanent electric dipole moment of thorium monoxide, ThO

Wang

Steimle

2011

The Journal of Chemical Physics

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The optical Stark spectrum of the E(0+) − X1Σ+ (1,0) band of thorium monoxide, ThO, was recorded and analyzed to determine the permanent electric dipole moments, μ, for the E(0+) (v = 1) and X1Σ+ (v = 0) states. Values of 2.782 ± 0.012 D (X) and 3.534 ± 0.010 D (E) were obtained. The uncertainties are 2σ statistical error. The systematic errors are estimated to be less than 1%. The experimental results are used to access the quality of electronic structure calculations of the properties of the X1Σ+ (v = 0) state.

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The pure rotational spectrum of the actinide-containing compound thorium monoxide

Abstract: The J = 1-0 pure rotational transition, together with hyperfine structure where appropriate, has been recorded for all three naturally occurring isotopomers of the actinide-containing compound thorium monoxide ((232)Th(16)O, (232)Th(17)O and (232)Th(18)O).

Cited by 38 publications

References 17 publications

Computed Vibrational Frequencies of Actinide Oxides AnO^0/+/2+ and AnO₂^0/+/2+ (An = Th, Pa, U, Np, Pu, Am, Cm)

Computed Vibrational Frequencies of Actinide Oxides AnO^0/+/2+ and AnO₂^0/+/2+ (An = Th, Pa, U, Np, Pu, Am, Cm)

The pure rotational spectrum of thorium monosulfide, ThS

Communication: The permanent electric dipole moment of thorium monoxide, ThO

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The pure rotational spectrum of the actinide-containing compound thorium monoxide

Abstract: The J = 1-0 pure rotational transition, together with hyperfine structure where appropriate, has been recorded for all three naturally occurring isotopomers of the actinide-containing compound thorium monoxide ((232)Th(16)O, (232)Th(17)O and (232)Th(18)O).

Cited by 38 publications

References 17 publications

Computed Vibrational Frequencies of Actinide Oxides AnO0/+/2+ and AnO20/+/2+ (An = Th, Pa, U, Np, Pu, Am, Cm)

Computed Vibrational Frequencies of Actinide Oxides AnO0/+/2+ and AnO20/+/2+ (An = Th, Pa, U, Np, Pu, Am, Cm)

The pure rotational spectrum of thorium monosulfide, ThS

Communication: The permanent electric dipole moment of thorium monoxide, ThO

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Computed Vibrational Frequencies of Actinide Oxides AnO^0/+/2+ and AnO₂^0/+/2+ (An = Th, Pa, U, Np, Pu, Am, Cm)

Computed Vibrational Frequencies of Actinide Oxides AnO^0/+/2+ and AnO₂^0/+/2+ (An = Th, Pa, U, Np, Pu, Am, Cm)