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Title: Fourier Transform Spectroscopy of the A {sup 3}Π– X {sup 3}Σ{sup −} Transition of OH{sup +}

Abstract

The OH{sup +} ion is of critical importance to the chemistry in the interstellar medium and is a prerequisite for the generation of more complex chemical species. Submillimeter and ultraviolet observations rely on high quality laboratory spectra. Recent measurements of the fundamental vibrational band and previously unanalyzed Fourier transform spectra of the near-ultraviolet A {sup 3}Π− X {sup 3}Σ{sup −} electronic spectrum, acquired at the National Solar Observatory at Kitt Peak in 1989, provide an excellent opportunity to perform a global fit of the available data. These new optical data are approximately four times more precise as compared to the previous values. The fit to the new data provides updated molecular constants, which are necessary to predict the OH{sup +} transition frequencies accurately to support future observations. These new constants are the first published using the modern effective Hamiltonian for a linear molecule. These new molecular constants allow for easy simulation of transition frequencies and spectra using the PGOPHER program. The new constants improve simulations of higher J -value infrared transitions, and represent an improvement of an order of magnitude for some constants pertaining to the optical transitions.

Authors:
;  [1]
  1. Department of Chemistry and Biochemistry, Old Dominion University, Norfolk, VA 23529 (United States)
Publication Date:
OSTI Identifier:
22663624
Resource Type:
Journal Article
Resource Relation:
Journal Name: Astrophysical Journal; Journal Volume: 840; Journal Issue: 2; Other Information: Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
79 ASTROPHYSICS, COSMOLOGY AND ASTRONOMY; APPROXIMATIONS; COMPARATIVE EVALUATIONS; FOURIER TRANSFORMATION; HAMILTONIANS; HYDROXIDES; IONS; MOLECULAR IONS; MOLECULES; SIMULATION; SPECTRA; SPECTROSCOPY; ULTRAVIOLET RADIATION; VIBRATIONAL STATES

Citation Formats

Hodges, James N., and Bernath, Peter F.. Fourier Transform Spectroscopy of the A {sup 3}Π– X {sup 3}Σ{sup −} Transition of OH{sup +}. United States: N. p., 2017. Web. doi:10.3847/1538-4357/AA6BF5.
Hodges, James N., & Bernath, Peter F.. Fourier Transform Spectroscopy of the A {sup 3}Π– X {sup 3}Σ{sup −} Transition of OH{sup +}. United States. doi:10.3847/1538-4357/AA6BF5.
Hodges, James N., and Bernath, Peter F.. Wed . "Fourier Transform Spectroscopy of the A {sup 3}Π– X {sup 3}Σ{sup −} Transition of OH{sup +}". United States. doi:10.3847/1538-4357/AA6BF5.
@article{osti_22663624,
title = {Fourier Transform Spectroscopy of the A {sup 3}Π– X {sup 3}Σ{sup −} Transition of OH{sup +}},
author = {Hodges, James N. and Bernath, Peter F.},
abstractNote = {The OH{sup +} ion is of critical importance to the chemistry in the interstellar medium and is a prerequisite for the generation of more complex chemical species. Submillimeter and ultraviolet observations rely on high quality laboratory spectra. Recent measurements of the fundamental vibrational band and previously unanalyzed Fourier transform spectra of the near-ultraviolet A {sup 3}Π− X {sup 3}Σ{sup −} electronic spectrum, acquired at the National Solar Observatory at Kitt Peak in 1989, provide an excellent opportunity to perform a global fit of the available data. These new optical data are approximately four times more precise as compared to the previous values. The fit to the new data provides updated molecular constants, which are necessary to predict the OH{sup +} transition frequencies accurately to support future observations. These new constants are the first published using the modern effective Hamiltonian for a linear molecule. These new molecular constants allow for easy simulation of transition frequencies and spectra using the PGOPHER program. The new constants improve simulations of higher J -value infrared transitions, and represent an improvement of an order of magnitude for some constants pertaining to the optical transitions.},
doi = {10.3847/1538-4357/AA6BF5},
journal = {Astrophysical Journal},
number = 2,
volume = 840,
place = {United States},
year = {Wed May 10 00:00:00 EDT 2017},
month = {Wed May 10 00:00:00 EDT 2017}
}
  • High resolution Fourier-transform spectroscopy data of term values in the spin-orbit (SO) coupled first excited A {sup 1}Σ{sup +} and b{sup 3}Π{sub 0±} states in KCs were obtained from (4){sup 1}Σ{sup +} → A {sup 1}Σ{sup +} − b {sup 3}Π, A {sup 1}Σ{sup +} − b {sup 3}Π → X{sup 1}Σ{sup +}, and (1){sup 3}Δ{sub 1} → b{sup 3}Π{sub 0±} spectra of laser-induced fluorescence (LIF). About 3000 new rovibronic term values of the A {sup 1}Σ{sup +} and b {sup 3}Π{sub Ω} states were obtained with an uncertainty about 0.01 cm{sup −1} and added to the previously obtained 3439 term values in Kruzins et al. [Phys. Rev.more » A 81, 042509 (2010)] and 30 term values of the b {sup 3}Π{sub 0{sup +}} state levels below the A {sup 1}Σ{sup +} state in Tamanis et al. [Phys. Rev. A 82, 032506 (2010)]. The data field was extended considerably, going down to vibrational level v{sub b} = 0 and up in energy to 13 814 cm{sup −1}, as compared to previously achieved v{sub b} = 14 and E = 13 250 cm{sup −1}. Overall 6431 e-symmetry term values of {sup 39}K{sup 133}Cs were included in 4 × 4 coupled-channel deperturbation analysis. The analytical Morse-Long-Range (MLR) function yielded empirical diabatic potentials for the A {sup 1}Σ{sup +} and b {sup 3}Π{sub 0{sup +}} states while the morphing of the SO ab initio points [J. T. Kim et al., J. Mol. Spectrosc. 256, 57 (2009)] provided the empirical diagonal and off-diagonal SO functions. Overall 98.5% of the fitted term values were reproduced with a rms (root mean square) uncertainty of 0.004 cm{sup −1}. The reliability of the model is proved by a good agreement of predicted and measured term values of the {sup 41}K{sup 133}Cs isotopologue, as well as of measured and calculated intensities of (4){sup 1}Σ{sup +} → A {sup 1}Σ{sup +} − b {sup 3}Π LIF progressions. Direct-potential-fit of low-lying v{sub b} levels of the b {sup 3}Π{sub 0{sup −}} component yielded the MLR potential which represents the 204 f-symmetry experimental term values with a rms uncertainty of 0.002 cm{sup −1}. The Ω-doubling of the b {sup 3}Π{sub 0} sub-state demonstrates a pronounced v{sub b}-dependent increase.« less
  • The article presents a study of the strongly spin-orbit coupled singlet A{sup 1}Σ{sup +} and triplet b{sup 3}Π states of the RbCs molecule, which provide an efficient optical path to transfer ultracold molecules to their rovibrational ground state. Fourier-transform A{sup 1}Σ{sup +} − b{sup 3}Π → X{sup 1}Σ{sup +} and (4){sup 1}Σ{sup +} → A{sup 1}Σ{sup +} − b{sup 3}Π laser-induced fluorescence (LIF) spectra were recorded for the natural mixture of the {sup 85}Rb{sup 133}Cs and {sup 87}Rb{sup 133}Cs isotopologues produced in a heat pipe oven. Overall 8730 rovibronic term values of A{sup 1}Σ{sup +} and b{sup 3}Π states weremore » determined with an uncertainty of 0.01 cm{sup −1} in the energy range [9012, 14087] cm{sup −1}, covering rotational quantum numbers J ∈ [6, 324]. An energy-based deperturbation analysis performed in the framework of the four A{sup 1}Σ{sup +} − b{sup 3}Π{sub Ω=0,1,2} coupled-channels approach reproduces 97% of the experimental term values of both isotopologues with a standard deviation of 0.0036 cm{sup −1}. The reliability of the deperturbed mass-invariant potentials and spin-orbit coupling functions of the interacting A{sup 1}Σ{sup +} and b{sup 3}Π states is additionally proved by a good reproduction of the A − b → X and (4){sup 1}Σ{sup +} → A − b relative intensity distributions. The achieved accuracy of the A − b complex description allowed us to use the latter to assign the observed (5){sup 1}Σ{sup +} → A − b and (3){sup 1}Π → A − b transitions. As is demonstrated, LIF to the A − b complex becomes as informative as to the ground X{sup 1}Σ{sup +} state, which is confirmed by comparing the results of (4){sup 1}Σ{sup +} state analysis based on (4){sup 1}Σ{sup +} → A − b LIF with the data from V. Zuters et al. [Phys. Rev. A 87, 022504 (2013)] based on (4){sup 1}Σ{sup +} → X LIF.« less
  • Fourier-transform A{sup 1}Σ{sup +} − b{sup 3}Π → X{sup 1}Σ{sup +} laser-induced fluorescence spectra were recorded for the natural mixture of {sup 39,41}K{sup 85,87}Rb isotopologues produced in a heatpipe oven. Overall 4200 rovibronic term values of the spin-orbit coupled A{sup 1}Σ{sup +} and b{sup 3}Π states were determined with an uncertainty of about 0.01 cm{sup −1} in the energy range [10 850, 14 200] cm{sup −1} covering rotational quantum numbers J′ ∈ [3, 280]. Direct deperturbation analysis of the A ∼ b complex performed within the framework of the A{sup 1}Σ{sup +} ∼ b{sup 3}Π{sub Ω=0,1,2} coupled-channel approach reproduced experimental data withmore » a standard deviation of 0.004 cm{sup −1}. Initial parameters of the internuclear potentials and spin-orbit coupling functions along with the relevant transition dipole moments were obtained by performing the quasi-relativistic electronic structure calculations. The mass-invariant molecular parameters obtained from the fit were used to predict energy and radiative properties of the A ∼ b complex for low J levels of {sup 39}K{sup 85}Rb as well as for {sup 41}K{sup 87}Rb isotopologues, allowing us to identify the most reasonable candidates for the stimulated Raman transitions between the initial uppermost vibrational levels of the a{sup 3}Σ{sup +} and X{sup 1}Σ{sup +} states, the intermediate levels of the A ∼ b complex, and the lowest absolute ground X{sup 1}Σ{sup +}(v = 0, J = 0) state.« less
  • The vector correlation between the alignment of reactant N{sub 2} (A {sup 3}Σ{sub u}{sup +}) and the alignment of product NO (A {sup 2}Σ{sup +}) rotation has been studied in the energy transfer reaction of aligned N{sub 2} (A {sup 3}Σ{sub u}{sup +}) + NO (X {sup 2}Π) → NO (A {sup 2}Σ{sup +}) + N{sub 2} (X {sup 1}Σ{sub g}{sup +}) under the crossed beam condition at a collision energy of ∼0.07 eV. NO (A {sup 2}Σ{sup +}) emission in the two linear polarization directions (i.e., parallel and perpendicular with respect to the relative velocity vector v{sub R}) hasmore » been measured as a function of the alignment of N{sub 2} (A {sup 3}Σ{sub u}{sup +}) along its molecular axis in the collision frame. The degree of polarization of NO (A {sup 2}Σ{sup +}) emission is found to depend on the alignment angle (θ{sub v{sub R}}) of N{sub 2} (A {sup 3}Σ{sub u}{sup +}) in the collision frame. The shape of the steric opacity function at the two polarization conditions turns out to be extremely different from each other: The steric opacity function at the parallel polarization condition is more favorable for the oblique configuration of N{sub 2} (A {sup 3}Σ{sub u}{sup +}) at an alignment angle of θ{sub v{sub R}} ∼ 45° as compared with that at the perpendicular polarization condition. The alignment of N{sub 2} (A {sup 3}Σ{sub u}{sup +}) is found to give a significant effect on the alignment of NO (A {sup 2}Σ{sup +}) rotation in the collision frame: The N{sub 2} (A {sup 3}Σ{sub u}{sup +}) configuration at an oblique alignment angle θ{sub v{sub R}} ∼ 45° leads to a parallel alignment of NO (A {sup 2}Σ{sup +}) rotation (J-vector) with respect to v{sub R}, while the axial and sideways configurations of N{sub 2} (A {sup 3}Σ{sub u}{sup +}) lead to a perpendicular alignment of NO (A {sup 2}Σ{sup +}) rotation with respect to v{sub R}. These stereocorrelated alignments of the product rotation have a good correlation with the stereocorrelated reactivity observed in the multi-dimensional steric opacity function [H. Ohoyama and S. Maruyama, J. Chem. Phys. 137, 064311 (2012)].« less