Theoretical study of the rovibrational spectrum of H2O–H2

Wang, Xiaogang; Carrington, Tucker

doi:10.1063/1.3533230

Cited by 57 publications

(72 citation statements)

References 54 publications

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“…This PES is independent of nuclear masses and can be employed for any water–hydrogen isotopologue. Its high accuracy has been spectacularly confirmed very recently by a number of comparisons between theory and experiment including inelastic total and differential cross‐sections (Yang et al 2010, 2011), pressure broadening cross‐sections (Wiesenfeld & Faure 2010), elastic integral cross‐sections (Belpassi et al 2010) and the spectrum of the van der Waals complex (van der Avoird & Nesbitt 2011; van der Avoird et al 2011; Wang & Carrington 2011).…”

Section: Scattering Calculationsmentioning

confidence: 88%

Rotational excitation of mono- and doubly-deuterated water by hydrogen molecules

Fauré¹,

Wiesenfeld²,

Scribano³

et al. 2011

Monthly Notices of the Royal Astronomical Society

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International audienceRate coefficients for rotational transitions in HDO and D2O induced by H-2 collisions below 300 K are presented. Calculations have been performed at the close-coupling and coupled-states levels with the deuterated variants of the H2O-H-2 interaction potential of Valiron et al. The HDO-H-2 and D2O-H-2 rate coefficients are compared to the corresponding rate coefficients for HDO-He and H2O-H-2, respectively. Significant differences are observed. In particular the new HDO rate coefficients are found to be significantly larger (by up to three orders of magnitude) than the corresponding HDO-He rate coefficients. The impact of the new HDO rate coefficients is examined with the help of non-LTE radiative transfer calculations. A number of potential HDO maser lines are finally identified, in particular the 80.6 GHz (1(1,0)-1(1,1)) transition

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Section: Scattering Calculationsmentioning

confidence: 88%

Rotational excitation of mono- and doubly-deuterated water by hydrogen molecules

Fauré¹,

Wiesenfeld²,

Scribano³

et al. 2011

Monthly Notices of the Royal Astronomical Society

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“…The high accuracy of these H 2 -H 2 O PES's has also been confirmed recently by a number of comparisons between theory and experiment including inelastic differential cross sections, 26 pressure broadening cross sections, 30,37 elastic integral cross sections, 18 and IR spectra of the complex. 15,17,21 In the present work, we use two different vibrationally averaged 5D PES's, with (i) both H 2 and H 2 O monomers in their ground vibrational state (as discussed in Valiron et al 1 ) and (ii) ground state H 2 (v = 0) and H 2 O in its doubly excited |02 − ) state, utilizing the wavefunction of Lodi and Tennyson. 49,50 Both ground and excited state 5D potentials are expressed as a 149 term angular expansion, 1 with coupled spherical harmonics in polar angles for (i) the center of mass vector R pointing from H 2 O to H 2 and (ii) the H 2 axis.…”

Section: A Potential Surfacesmentioning

confidence: 99%

“…24,26,[28][29][30] The need for high level predictive understanding for such high pressure/temperature combustion phenomena is clearly important, which in turn depends pivotally on benchmark accuracy of the full 9D potential H 2 + H 2 O energy surface. 1,15,17,[20][21][22][23] Of particular interest in the interstellar medium (ISM) is the corresponding weakly bound complex, H 2 -H 2 O, due in part to predominance of atomic and molecular hydrogen in the universe. 31 Indeed, certain regions of the ISM depleted in deep ultraviolet radiation tend to have appreciable concentrations of H 2 molecules rather than H atoms, 32 which can in fact trigger chemical synthesis into higher molecular weight species.…”

Section: Introductionmentioning

confidence: 99%

“…The current work focuses on spectroscopy, dynamics, and interaction potentials for H 2 + H 2 O, 1,13,[15][16][17][18][19][20][21] which proves to be relevant in a wide range of terrestrial and extraterrestrial venues. 2,[22][23][24][25][26] In high temperature H 2 /O 2 combustion, for example, collisions of the highly energized product H 2 O molecules with H 2 reactant provide an important mechanism for heat flow as well as establishing local thermodynamic equilibrium in the flames.…”

Section: Introductionmentioning

confidence: 99%

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Overtone vibrational spectroscopy in H2-H2O complexes: A combined high level theoretical ab initio, dynamical and experimental study

Ziemkiewicz

Pluetzer

Nesbitt

et al. 2012

The Journal of Chemical Physics

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First results are reported on overtone (v OH = 2 ← 0) spectroscopy of weakly bound H 2 -H 2 O complexes in a slit supersonic jet, based on a novel combination of (i) vibrationally mediated predissociation of H 2 -H 2 O, followed by (ii) UV photodissociation of the resulting H 2 O, and (iii) UV laser induced fluorescence on the nascent OH radical. In addition, intermolecular dynamical calculations are performed in full 5D on the recent ab initio intermolecular potential of Valiron et al. [J. Chem. Phys. 129, 134306 (2008)] in order to further elucidate the identity of the infrared transitions detected. Excellent agreement is achieved between experimental and theoretical spectral predictions for the most strongly bound van der Waals complex consisting of ortho (I = 1) H 2 and ortho (I = 1) H 2 O (oH 2 -oH 2 O). Specifically, two distinct bands are seen in the oH 2 -oH 2 O spectrum, corresponding to internal rotor states in the upper vibrational manifold of and rotational character. However, none of the three other possible nuclear spin modifications (pH 2 -oH 2 O, pH 2 -pH 2 O, or oH 2 -pH 2 O) are observed above current signal to noise level, which for the pH 2 complexes is argued to arise from displacement by oH 2 in the expansion mixture to preferentially form the more strongly bound species. Direct measurement of oH 2 -oH 2 O vibrational predissociation in the time domain reveals lifetimes of 15(2) ns and <5(2) ns for the and states, respectively. Theoretical calculations permit the results to be interpreted in terms of near resonant energy levels and intermolecular alignment of the H 2 and H 2 O wavefunctions, providing insight into predissociation dynamical pathways from these metastable levels.

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“…Furthermore, they performed CCSD(T) calculations for H 2 O and H 2 structures with non-equilibrium geometries to generate a 9D PES, and used the ground state vibrational eigenfunctions of the two molecules to average this PES to obtain a 5D PES. The success of such an explicitly correlated and vibrationally averaged PES is demonstrated by the two recent works of Wang and Carrington 22 and van der Avoird and Nesbitt 23 who employed this PES to perform exact bound state calculations for the H 2 O-H 2 complex. They both obtained results that were in excellent agreement with experimental data.…”

Section: Introductionmentioning

confidence: 99%

“Adiabatic-hindered-rotor” treatment of the parahydrogen-water complex

Zeng

Roy

et al. 2011

The Journal of Chemical Physics

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Inspired by a recent successful adiabatic-hindered-rotor treatment for parahydrogen pH(2) in CO(2)-H(2) complexes [H. Li, P.-N. Roy, and R. J. Le Roy, J. Chem. Phys. 133, 104305 (2010); H. Li, R. J. Le Roy, P.-N. Roy, and A. R. W. McKellar, Phys. Rev. Lett. 105, 133401 (2010)], we apply the same approximation to the more challenging H(2)O-H(2) system. This approximation reduces the dimension of the H(2)O-H(2) potential from 5D to 3D and greatly enhances the computational efficiency. The global minimum of the original 5D potential is missing from the adiabatic 3D potential for reasons based on solution of the hindered-rotor Schrödinger equation of the pH(2). Energies and wave functions of the discrete rovibrational levels of H(2)O-pH(2) complexes obtained from the adiabatic 3D potential are in good agreement with the results from calculations with the full 5D potential. This comparison validates our approximation, although it is a relatively cruder treatment for pH(2)-H(2)O than it is for pH(2)-CO(2). This adiabatic approximation makes large-scale simulations of H(2)O-pH(2) systems possible via a pairwise additive interaction model in which pH(2) is treated as a point-like particle. The poor performance of the diabatically spherical treatment of pH(2) rotation excludes the possibility of approximating pH(2) as a simple sphere in its interaction with H(2)O.

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Theoretical study of the rovibrational spectrum of H2O–H2

Cited by 57 publications

References 54 publications

Rotational excitation of mono- and doubly-deuterated water by hydrogen molecules

Rotational excitation of mono- and doubly-deuterated water by hydrogen molecules

Overtone vibrational spectroscopy in H2-H2O complexes: A combined high level theoretical ab initio, dynamical and experimental study

“Adiabatic-hindered-rotor” treatment of the parahydrogen-water complex

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