Two new tools for computer assisted assignment of rotational spectra with the PGOPHER program are presented, aimed particularly at spectra where many individual lines are resolved. The first tool tries many different assignments, presenting a small number for possible refinement and a preliminary version of this has already been presented. The second tool, the nearest lines plot (a new style of residual plot) provides a clear indication as to whether a trial calculation is plausible, and allows rapid assignment of sets of related lines. It gives good results even for dense spectra with no obvious structure and in the presence of multiple interfering absorptions. The effectiveness of these tools is demonstrated by the analysis of high resolution IR spectra of 8 bands of cis- and trans-1,2-dichloroethene where, including hot bands and isotopologues, 31 vibrational transitions and 158 316 individual lines have been analysed, including perturbations for the higher energy states. Walkthroughs are presented to show this process is rapid.
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http://dx.doi.org/10.1039/c8cp06493h | DOI Listing |
Absolute line strength measurements of hydroperoxyl (HO2) radical in the OO-stretching (ν3) fundamental band have been performed by means of mid-infrared time-resolved dual-comb spectroscopy. By employing two sets of dual-comb spectrometers, high-resolution time-resolved spectra of HO2 and HCl, formed in the photolysis reaction system of Cl2/CH3OH/O2, could be, respectively, measured near 1123 and 3059 cm-1. With kinetic simulations, spectral analysis of both HO2 and HCl, as well as the accurate line strength of the HCl R(9) transition at 3059.
View Article and Find Full Text PDFSpectrochim Acta A Mol Biomol Spectrosc
April 2023
Department of Physics, Institute of Science, Banaras Hindu University, Varanasi 221005, India.
The rotational line survey by ALMA (Atacama Large Millimeter/submillimeter Array) recently revealed the presence of i-CHCN (i-PrCN) and n-CHCN (n-PrCN) in 3-mm atmospheric window between 84 to 111 GHz towards the hot core region Sagittarius B2(N) (Sgr B2(N)). This was the first interstellar detection of a linear straight chain molecule. In this light, we report the rotational spectra of CH isomeric group in the same frequency range.
View Article and Find Full Text PDFJ Chem Phys
October 2022
Department of Chemistry, University of California at Riverside, Riverside, California 92521, USA.
Photo-predissociation of SH and SD radicals in the AΣ state is investigated using the high-n Rydberg atom time-of-flight technique. By measuring the photoproduct translational energy distributions as a function of excitation wavelength, contributions from overlapping AΣ (v') ← XΠ (v″) transitions can be separated, and the H/D + S(P) photofragment yield (PFY) spectra are obtained across various rovibrational levels (SH v' = 0-7 and SD v' = 0-8) of the AΣ ← XΠ bands. The upper AΣ state vibrational levels v' = 5-7 of SH and v' = 3-8 of SD are determined for the first time.
View Article and Find Full Text PDFJ Chem Phys
March 2022
School of Chemistry, University of Leeds, Leeds, United Kingdom.
Direct frequency comb spectroscopy was utilized to measure the vibrational absorption spectrum of diiodomethane, CHI, from 2960 to 3125 cm. The data were obtained using a CHI concentration of (6.8 ± 1.
View Article and Find Full Text PDFJ Chem Theory Comput
March 2022
Department of Physics and Astronomy, University College London, WC1E 6BT London, U.K.
An algorithm for the calculation of hyperfine structure and spectra of diatomic molecules based on the variational nuclear motion is presented. The hyperfine coupling terms considered are Fermi-contact, nuclear spin-electron spin dipole-dipole, nuclear spin-orbit, nuclear spin-rotation, and nuclear electric quadrupole interactions. Initial hyperfine-unresolved wave functions are obtained for a given set of potential energy curves and associated couplings by a variation solution of the nuclear-motion Schrödinger equation.
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