A new program for the assignment and fitting of dense rotational spectra based on spectral progressions: Application to the microwave spectrum of pivalic anhydride

Nathan Love; Anna K. Huff; Kenneth R. Leopold

doi:10.1016/j.jms.2020.111294

A new program for the assignment and fitting of dense rotational spectra based on spectral progressions: Application to the microwave spectrum of pivalic anhydride

Nathan Love, Anna K. Huff, Kenneth R. Leopold

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

10 Scopus citations

Abstract

A new computerized package for the rapid processing and analysis of dense rotational spectra is described. The package is based on the automated identification of user-specified spectral progressions and interacts with the operator through a simple graphical user interface. In addition to containing an algorithm for obtaining spectral assignments, the package includes a peak-finder with adjustable baseline drift compensation, seamless interfacing with Pickett's SPFIT and SPCAT programs, and a number of visualization features. The utility of the program is illustrated through its application to the analysis of new spectra of pivalic anhydride, (CH₃)₃CCOOCOC(CH₃)₃. Spectra of the parent, as well as all isotopologues with single heavy-atom substitution, are reported, as are calculations for the parent species at the M06-2X/6-311++G(3df,3pd) level of theory. The central oxygen atom is poorly located due to its proximity to the center of mass of the molecule, but a Kraitchman analysis of the fitted rotational constants otherwise provides a detailed structural characterization of the heavy-atom frame. The two carbonyl groups are not coplanar, but rather form a dihedral angle of 53.9(39) deg.

Original language	English (US)
Article number	111294
Journal	Journal of molecular spectroscopy
Volume	370
DOIs	https://doi.org/10.1016/j.jms.2020.111294
State	Published - Apr 2020

Bibliographical note

Funding Information:
This work was supported by the National Science Foundation (Grant No. CHE 1563324 ) and the Minnesota Supercomputing Institute. We are grateful to Brian Esselman (UW Madison), Helen Leung ( Amherst College ), Mark Marshall (Amherst College), Fan Xie ( University of Alberta ), and Yunji Xu (University of Alberta) for providing their experimental spectral files which were critical to the development and testing of DAPPERS.

Funding Information:
This work was supported by the National Science Foundation (Grant No. CHE 1563324) and the Minnesota Supercomputing Institute. We are grateful to Brian Esselman (UW Madison), Helen Leung (Amherst College), Mark Marshall (Amherst College), Fan Xie (University of Alberta), and Yunji Xu (University of Alberta) for providing their experimental spectral files which were critical to the development and testing of DAPPERS.

Publisher Copyright:
© 2020 Elsevier Inc.

Keywords

Autofitting
Molecular structure
Pivalic anhydride
Rotational spectra
Spectral progressions

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10.1016/j.jms.2020.111294

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@article{faf206ec57234f1eae651bb9f5107c18,

title = "A new program for the assignment and fitting of dense rotational spectra based on spectral progressions: Application to the microwave spectrum of pivalic anhydride",

abstract = "A new computerized package for the rapid processing and analysis of dense rotational spectra is described. The package is based on the automated identification of user-specified spectral progressions and interacts with the operator through a simple graphical user interface. In addition to containing an algorithm for obtaining spectral assignments, the package includes a peak-finder with adjustable baseline drift compensation, seamless interfacing with Pickett's SPFIT and SPCAT programs, and a number of visualization features. The utility of the program is illustrated through its application to the analysis of new spectra of pivalic anhydride, (CH3)3CCOOCOC(CH3)3. Spectra of the parent, as well as all isotopologues with single heavy-atom substitution, are reported, as are calculations for the parent species at the M06-2X/6-311++G(3df,3pd) level of theory. The central oxygen atom is poorly located due to its proximity to the center of mass of the molecule, but a Kraitchman analysis of the fitted rotational constants otherwise provides a detailed structural characterization of the heavy-atom frame. The two carbonyl groups are not coplanar, but rather form a dihedral angle of 53.9(39) deg.",

keywords = "Autofitting, Molecular structure, Pivalic anhydride, Rotational spectra, Spectral progressions",

author = "Nathan Love and Huff, \{Anna K.\} and Leopold, \{Kenneth R.\}",

note = "Funding Information: This work was supported by the National Science Foundation (Grant No. CHE 1563324 ) and the Minnesota Supercomputing Institute. We are grateful to Brian Esselman (UW Madison), Helen Leung ( Amherst College ), Mark Marshall (Amherst College), Fan Xie ( University of Alberta ), and Yunji Xu (University of Alberta) for providing their experimental spectral files which were critical to the development and testing of DAPPERS. Funding Information: This work was supported by the National Science Foundation (Grant No. CHE 1563324) and the Minnesota Supercomputing Institute. We are grateful to Brian Esselman (UW Madison), Helen Leung (Amherst College), Mark Marshall (Amherst College), Fan Xie (University of Alberta), and Yunji Xu (University of Alberta) for providing their experimental spectral files which were critical to the development and testing of DAPPERS. Publisher Copyright: {\textcopyright} 2020 Elsevier Inc.",

year = "2020",

month = apr,

doi = "10.1016/j.jms.2020.111294",

language = "English (US)",

volume = "370",

journal = "Journal of molecular spectroscopy",

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T1 - A new program for the assignment and fitting of dense rotational spectra based on spectral progressions

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AU - Huff, Anna K.

AU - Leopold, Kenneth R.

N1 - Funding Information: This work was supported by the National Science Foundation (Grant No. CHE 1563324 ) and the Minnesota Supercomputing Institute. We are grateful to Brian Esselman (UW Madison), Helen Leung ( Amherst College ), Mark Marshall (Amherst College), Fan Xie ( University of Alberta ), and Yunji Xu (University of Alberta) for providing their experimental spectral files which were critical to the development and testing of DAPPERS. Funding Information: This work was supported by the National Science Foundation (Grant No. CHE 1563324) and the Minnesota Supercomputing Institute. We are grateful to Brian Esselman (UW Madison), Helen Leung (Amherst College), Mark Marshall (Amherst College), Fan Xie (University of Alberta), and Yunji Xu (University of Alberta) for providing their experimental spectral files which were critical to the development and testing of DAPPERS. Publisher Copyright: © 2020 Elsevier Inc.

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N2 - A new computerized package for the rapid processing and analysis of dense rotational spectra is described. The package is based on the automated identification of user-specified spectral progressions and interacts with the operator through a simple graphical user interface. In addition to containing an algorithm for obtaining spectral assignments, the package includes a peak-finder with adjustable baseline drift compensation, seamless interfacing with Pickett's SPFIT and SPCAT programs, and a number of visualization features. The utility of the program is illustrated through its application to the analysis of new spectra of pivalic anhydride, (CH3)3CCOOCOC(CH3)3. Spectra of the parent, as well as all isotopologues with single heavy-atom substitution, are reported, as are calculations for the parent species at the M06-2X/6-311++G(3df,3pd) level of theory. The central oxygen atom is poorly located due to its proximity to the center of mass of the molecule, but a Kraitchman analysis of the fitted rotational constants otherwise provides a detailed structural characterization of the heavy-atom frame. The two carbonyl groups are not coplanar, but rather form a dihedral angle of 53.9(39) deg.

AB - A new computerized package for the rapid processing and analysis of dense rotational spectra is described. The package is based on the automated identification of user-specified spectral progressions and interacts with the operator through a simple graphical user interface. In addition to containing an algorithm for obtaining spectral assignments, the package includes a peak-finder with adjustable baseline drift compensation, seamless interfacing with Pickett's SPFIT and SPCAT programs, and a number of visualization features. The utility of the program is illustrated through its application to the analysis of new spectra of pivalic anhydride, (CH3)3CCOOCOC(CH3)3. Spectra of the parent, as well as all isotopologues with single heavy-atom substitution, are reported, as are calculations for the parent species at the M06-2X/6-311++G(3df,3pd) level of theory. The central oxygen atom is poorly located due to its proximity to the center of mass of the molecule, but a Kraitchman analysis of the fitted rotational constants otherwise provides a detailed structural characterization of the heavy-atom frame. The two carbonyl groups are not coplanar, but rather form a dihedral angle of 53.9(39) deg.

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KW - Rotational spectra

KW - Spectral progressions

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M1 - 111294

ER -

A new program for the assignment and fitting of dense rotational spectra based on spectral progressions: Application to the microwave spectrum of pivalic anhydride

Abstract

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Keywords

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