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Title: Imaging a multidimensional multichannel potential energy surface: Photodetachment of H (NH 3 ) and NH 4

Authors:
 [1];  [2];  [1];  [3];  [2]; ORCiD logo [1]
  1. Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, California 92093-0340, USA
  2. Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, USA
  3. School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, China
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1259738
Grant/Contract Number:
FG02-05ER15694
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 24; Related Information: CHORUS Timestamp: 2018-02-14 23:38:56; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics
Country of Publication:
United States
Language:
English

Citation Formats

Hu, Qichi, Song, Hongwei, Johnson, Christopher J., Li, Jun, Guo, Hua, and Continetti, Robert E.. Imaging a multidimensional multichannel potential energy surface: Photodetachment of H − (NH 3 ) and NH 4 −. United States: N. p., 2016. Web. doi:10.1063/1.4954187.
Hu, Qichi, Song, Hongwei, Johnson, Christopher J., Li, Jun, Guo, Hua, & Continetti, Robert E.. Imaging a multidimensional multichannel potential energy surface: Photodetachment of H − (NH 3 ) and NH 4 −. United States. doi:10.1063/1.4954187.
Hu, Qichi, Song, Hongwei, Johnson, Christopher J., Li, Jun, Guo, Hua, and Continetti, Robert E.. 2016. "Imaging a multidimensional multichannel potential energy surface: Photodetachment of H − (NH 3 ) and NH 4 −". United States. doi:10.1063/1.4954187.
@article{osti_1259738,
title = {Imaging a multidimensional multichannel potential energy surface: Photodetachment of H − (NH 3 ) and NH 4 −},
author = {Hu, Qichi and Song, Hongwei and Johnson, Christopher J. and Li, Jun and Guo, Hua and Continetti, Robert E.},
abstractNote = {},
doi = {10.1063/1.4954187},
journal = {Journal of Chemical Physics},
number = 24,
volume = 144,
place = {United States},
year = 2016,
month = 6
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1063/1.4954187

Citation Metrics:
Cited by: 5works
Citation information provided by
Web of Science

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  • An experimental study of the dissociative photodetachment (DPD) dynamics of HOCO{sup -} and DOCO{sup -} at a photon energy of 3.21 eV has been carried out to probe the potential energy surface of the HOCO free radical and the dynamics of the OH+CO{yields}H+CO{sub 2} reaction. These photoelectron-photofragment coincidence experiments allow the identification of photodetachment processes leading to the production of stable HOCO free radicals and both the H+CO{sub 2} and OH+CO dissociation channels on the neutral surface. Isotopic substitution by deuterium in the parent ion is observed to reduce the product branching ratio for the D+CO{sub 2} channel, consistent withmore » tunneling playing a role in this dissociation pathway. Other isotope effects on the detailed partitioning of kinetic energy between photoelectrons and photofragments are also discussed. The results are compared to recent theoretical predictions of this DPD process, and evidence for the involvement of vibrationally excited HOCO{sup -} anions is discussed.« less
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  • A general theoretical treatment of multichannel photodetachment is presented, with application to Cs$sup -$ photodetachment from 14,800 to 15,600 cm$sup -1$. The sharp and strong resonances near the first $sup 2$P states of the Cs atom, observed by Patterson et al., were reproduced by fitting eight physically meaningful parameters of a general theoretical framework. Predictions are also made concerning the branching ratios, the angular distribution, and the spin orientation of the detached electrons as well as the orientation of the excited neutral Cs atoms. (auth)
  • A regularized inverse method is developed to determine an accurate multidimensional potential energy surface directly from spectral or scattering data. The method properly handles the inherent underdeterminancy, instability and nonlinearity of the problem, and extracts a physically acceptable smooth solution. The method is implemented for Ar+OH(A [sup 2][summation][sup +]).
  • A general interpolation method for constructing smooth molecular potential energy surfaces (PES{close_quote}s) from {ital ab} {ital initio} data are proposed within the framework of the reproducing kernel Hilbert space and the inverse problem theory. The general expression for an {ital a} {ital posteriori} error bound of the constructed PES is derived. It is shown that the method yields globally smooth potential energy surfaces that are continuous and possess derivatives up to second order or higher. Moreover, the method is amenable to correct symmetry properties and asymptotic behavior of the molecular system. Finally, the method is generic and can be easilymore » extended from low dimensional problems involving two and three atoms to high dimensional problems involving four or more atoms. Basic properties of the method are illustrated by the construction of a one-dimensional potential energy curve of the He{endash}He van der Waals dimer using the exact quantum Monte Carlo calculations of Anderson {ital et} {ital al}. [J. Chem. Phys. {bold 99}, 345 (1993)], a two-dimensional potential energy surface of the HeCO van der Waals molecule using recent {ital ab} {ital initio} calculations by Tao {ital et} {ital al}. [J. Chem. Phys. {bold 101}, 8680 (1994)], and a three-dimensional potential energy surface of the H{sup +}{sub 3} molecular ion using highly accurate {ital ab} {ital initio} calculations of R{umlt o}hse {ital et} {ital al}. [J. Chem. Phys. {bold 101}, 2231 (1994)]. In the first two cases the constructed potentials clearly exhibit the correct asymptotic forms, while in the last case the constructed potential energy surface is in excellent agreement with that constructed by R{umlt o}hse {ital et} {ital al}. using a low order polynomial fitting procedure. {copyright} {ital 1996 American Institute of Physics.}« less