<i>Ab initio</i> global potential-energy surface for H5+→H3++H2

Xie, Zhen; Braams, Bastiaan J.; Bowman, Joel M.

doi:10.1063/1.1927529

Cited by 117 publications

(240 citation statements)

References 26 publications

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“…To date, several full dimensional potential energy surfaces (PESs) for H 5 + are available [8][9][10]. In this Rapid Communication we use the accurate triatomics in molecules based analytical PES [9], fitted to high-level ab initio points [11], together with the electric dipole moment surface recently reported and used to perform spectra simulations at zero temperature [12].…”

Section: The Hmentioning

confidence: 99%

Infrared spectrum of H5+and D5+: The simplest shared-proton model

et al. 2011

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We present a two-dimensional collinear, adiabatic model to describe the motion of a proton in between two hydrogen molecules which adjust their elongation to trace a minimum-energy path. Together with bound states, the predissociative, vibrationally excited states involved in the electric dipole transitions are characterized. The main qualitative features of the infrared spectra of H 5 + and its deuterated variant are discussed, and the effect of the temperature of the clusters is analyzed. To just account for the proton transfer between the two H 2 moieties, we present an extremely simplified two-dimensional (2D) model which incorporates the effect of the temperature.Considering three collinear masses M 1 -M 0 -M 2 , denoting by d 1 and d 2 , the distances from the central mass to the extreme ones, and employing the coordinates R = d 1 + d 2 (0 R ∞) and r = d 1 − d 2 (−R r R) the kinetic energy operator in the center of mass system becomeŝ

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Section: The Hmentioning

confidence: 99%

Infrared spectrum of H5+and D5+: The simplest shared-proton model

et al. 2011

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“…18 This demand is motivating work on ab initio methods capable of yielding the desired accuracy 4,5,[19][20][21] and the search for new methodological approaches. [22][23][24][25][26][27] Interest also continues in methods for deducing accurate potential energy functions directly from observed vibrational spectra. [28][29][30] The best available potential energy curves are also useful in the modeling of "universal" potential energy functions.…”

Section: Introductionmentioning

confidence: 99%

Accurate ab initio potential energy curve of F2. III. The vibration rotation spectrum

Bytautas

Matsunaga

Nagata

et al. 2007

The Journal of Chemical Physics

134

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An analytical expression is found for the accurate ab initiopotential energy curve of the fluorine molecule that has been determined in the preceding two papers. With it, the vibrational and rotational energy levels of F2 are calculated using the discrete variable representation. The comparison of this theoretical spectrum with the experimental spectrum, which had been measured earlier using high-resolution electronic spectroscopy, yields a mean absolute deviation of about 5cm−1 over the 22 levels. The dissociation energy with respect to the lowest vibrational energy is calculated within 30cm−1 of the experimental value of 12953±8cm−1. The reported agreement of the theoretical spectrum and dissociation energy with experiment is contingent upon the inclusion of the effects of core-generated electron correlation,spin-orbit coupling, and scalar relativity. The Dunham analysis [Phys. Rev.41, 721 (1932)] of the spectrum is found to be very accurate. New values are given for the spectroscopic constants. KeywordsAb initio calculations, Dissociation energies, Polynomials, Dissociation, Electron correlation calculations Disciplines Chemistry CommentsThe following article appeared in Journal of Chemical Physics 127 (2007) An analytical expression is found for the accurate ab initio potential energy curve of the fluorine molecule that has been determined in the preceding two papers. With it, the vibrational and rotational energy levels of F 2 are calculated using the discrete variable representation. The comparison of this theoretical spectrum with the experimental spectrum, which had been measured earlier using high-resolution electronic spectroscopy, yields a mean absolute deviation of about 5 cm −1 over the 22 levels. The dissociation energy with respect to the lowest vibrational energy is calculated within 30 cm −1 of the experimental value of 12 953± 8 cm −1 . The reported agreement of the theoretical spectrum and dissociation energy with experiment is contingent upon the inclusion of the effects of core-generated electron correlation, spin-orbit coupling, and scalar relativity. The Dunham analysis ͓Phys. Rev. 41, 721 ͑1932͔͒ of the spectrum is found to be very accurate. New values are given for the spectroscopic constants.

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“…In particular, new methods of treating the rovibrational symmetry of these fluxional systems have had to be developed. 92,93 Obtaining reliable analytic fits to a PES, which shows ten [94][95][96] energetically accessible stationary points, have proved difficult. 97 These systems display unusual spectroscopic properties 98 and new methods for treating the nuclear motion problem have been developed.…”

Section: Hydrogenic Systems As Benchmarksmentioning

confidence: 99%

Perspective: Accurate ro-vibrational calculations on small molecules

Tennyson

2016

The Journal of Chemical Physics

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In what has been described as the fourth age of quantum chemistry, variational nuclear motion programs are now routinely being used to obtain the vibration-rotation levels and corresponding wavefunctions of small molecules to the sort of high accuracy demanded by comparison with spectroscopy. In this perspective, I will discuss the current state-of-the-art which, for example, shows that these calculations are increasingly competitive with measurements or, indeed, replacing them and thus becoming the primary source of data on key processes. To achieve this accuracy ab initio requires consideration of small effects, routinely ignored in standard calculations, such as those due to quantum electrodynamics. Variational calculations are being used to generate huge lists of transitions which provide the input for models of radiative transport through hot atmospheres and to fill in or even replace measured transition intensities. Future prospects such as the study of molecular states near dissociation, which can provide a link with low-energy chemical reactions, are discussed. Published by AIP Publishing. [http://dx

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Ab initio global potential-energy surface for H5+→H3++H2

Cited by 117 publications

References 26 publications

Infrared spectrum of H5+and D5+: The simplest shared-proton model

Infrared spectrum of H5+and D5+: The simplest shared-proton model

Accurate ab initio potential energy curve of F2. III. The vibration rotation spectrum

Perspective: Accurate ro-vibrational calculations on small molecules

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