Motional narrowing of the rotational spectrum of trifluoropropyne at 6550 cm -1 by intramolecular vibrational energy redistribution

Kevin O. Douglass; Brian C. Dian; Gordon G. Brown; James E. Johns; Pradeep M. Nair; Brooks H. Pate

doi:10.1063/1.1780164

Motional narrowing of the rotational spectrum of trifluoropropyne at 6550 cm ^-1 by intramolecular vibrational energy redistribution

Kevin O. Douglass, Brian C. Dian, Gordon G. Brown, James E. Johns, Pradeep M. Nair, Brooks H. Pate

Chemistry (Twin Cities)

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

9 Scopus citations

Abstract

The principles of dynamic rotational spectroscopy for the vibrationally excited symmetric top molecule trifluoropropyne (TFP, CF ₃CCH) were analyzed using Fourier transform microwave (FTMW) spectroscopy. The eigenstate-resolved rotational spectra were obtained in the high state density region of the acetylenic CH stretch first overtone of TFP at 6550 cm ^-1. The effect of intramolecular vibrational energy redistribution (IVR) exchange narrowing was possible due to the availability of the vibrational dependence of the rotational constants. It is found that narrowing of the spectrum by fast IVR within a single isomer is important to the application of dynamic rotational spectroscopy to isomerizing systems.

Original language	English (US)
Pages (from-to)	6845-6854
Number of pages	10
Journal	Journal of Chemical Physics
Volume	121
Issue number	14
DOIs	https://doi.org/10.1063/1.1780164
State	Published - Oct 8 2004

Publisher link

10.1063/1.1780164

Find It

Find It at U of M Libraries

Cite this

@article{a1839cd5927e452b8c018e5fd4a6dc1c,

title = "Motional narrowing of the rotational spectrum of trifluoropropyne at 6550 cm -1 by intramolecular vibrational energy redistribution",

abstract = "The principles of dynamic rotational spectroscopy for the vibrationally excited symmetric top molecule trifluoropropyne (TFP, CF 3CCH) were analyzed using Fourier transform microwave (FTMW) spectroscopy. The eigenstate-resolved rotational spectra were obtained in the high state density region of the acetylenic CH stretch first overtone of TFP at 6550 cm -1. The effect of intramolecular vibrational energy redistribution (IVR) exchange narrowing was possible due to the availability of the vibrational dependence of the rotational constants. It is found that narrowing of the spectrum by fast IVR within a single isomer is important to the application of dynamic rotational spectroscopy to isomerizing systems.",

author = "Douglass, {Kevin O.} and Dian, {Brian C.} and Brown, {Gordon G.} and Johns, {James E.} and Nair, {Pradeep M.} and Pate, {Brooks H.}",

year = "2004",

month = oct,

day = "8",

doi = "10.1063/1.1780164",

language = "English (US)",

volume = "121",

pages = "6845--6854",

journal = "Journal of Chemical Physics",

issn = "0021-9606",

publisher = "American Institute of Physics Publising LLC",

number = "14",

}

TY - JOUR

T1 - Motional narrowing of the rotational spectrum of trifluoropropyne at 6550 cm -1 by intramolecular vibrational energy redistribution

AU - Douglass, Kevin O.

AU - Dian, Brian C.

AU - Brown, Gordon G.

AU - Johns, James E.

AU - Nair, Pradeep M.

AU - Pate, Brooks H.

PY - 2004/10/8

Y1 - 2004/10/8

N2 - The principles of dynamic rotational spectroscopy for the vibrationally excited symmetric top molecule trifluoropropyne (TFP, CF 3CCH) were analyzed using Fourier transform microwave (FTMW) spectroscopy. The eigenstate-resolved rotational spectra were obtained in the high state density region of the acetylenic CH stretch first overtone of TFP at 6550 cm -1. The effect of intramolecular vibrational energy redistribution (IVR) exchange narrowing was possible due to the availability of the vibrational dependence of the rotational constants. It is found that narrowing of the spectrum by fast IVR within a single isomer is important to the application of dynamic rotational spectroscopy to isomerizing systems.

AB - The principles of dynamic rotational spectroscopy for the vibrationally excited symmetric top molecule trifluoropropyne (TFP, CF 3CCH) were analyzed using Fourier transform microwave (FTMW) spectroscopy. The eigenstate-resolved rotational spectra were obtained in the high state density region of the acetylenic CH stretch first overtone of TFP at 6550 cm -1. The effect of intramolecular vibrational energy redistribution (IVR) exchange narrowing was possible due to the availability of the vibrational dependence of the rotational constants. It is found that narrowing of the spectrum by fast IVR within a single isomer is important to the application of dynamic rotational spectroscopy to isomerizing systems.

UR - http://www.scopus.com/inward/record.url?scp=7544235572&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=7544235572&partnerID=8YFLogxK

U2 - 10.1063/1.1780164

DO - 10.1063/1.1780164

M3 - Article

C2 - 15473742

AN - SCOPUS:7544235572

SN - 0021-9606

VL - 121

SP - 6845

EP - 6854

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

IS - 14

ER -

Motional narrowing of the rotational spectrum of trifluoropropyne at 6550 cm ^-1 by intramolecular vibrational energy redistribution

Abstract

Publisher link

Find It

Other files and links

Fingerprint

Cite this