The ground state vibrational structure of SCCl2: Observation of backbone IVR

R. Bigwood; B. Milam; M. Gruebele

doi:10.1016/S0009-2614(98)00190-0

The ground state vibrational structure of SCCl₂: Observation of backbone IVR

R. Bigwood, B. Milam, M. Gruebele

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

Abstract

Vibrationally excited SCCl₂ is a model system for energy redistribution among backbone vibrational modes. Over 200 transitions in the X̃←B̃ dispersed fluorescence spectrum of thiophosgene have been observed to map the ground electronic surface up to 15000 cm^-1. An analytical six-dimensional potential surface derived from ab initio calculations has been fitted directly to about 100 of the transitions to provide an experimentally derived surface for intramolecular vibrational energy redistribution (IVR) quantum dynamics calculations. Higher resolution stimulated emission pumping spectra from different vibrational levels in the B̃ state reveal a complex progression from unfragmented/slightly Fermi-resonant states, to highly fragmented states above v₁=8.

Original language	English (US)
Pages (from-to)	333-341
Number of pages	9
Journal	Chemical Physics Letters
Volume	287
Issue number	3-4
DOIs	https://doi.org/10.1016/S0009-2614(98)00190-0
State	Published - May 1 1998

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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Cite this

@article{c9830e228fd8482dbb46d1de6da41b36,

title = "The ground state vibrational structure of SCCl2: Observation of backbone IVR",

abstract = "Vibrationally excited SCCl2 is a model system for energy redistribution among backbone vibrational modes. Over 200 transitions in the {\~X}←{\~B} dispersed fluorescence spectrum of thiophosgene have been observed to map the ground electronic surface up to 15000 cm-1. An analytical six-dimensional potential surface derived from ab initio calculations has been fitted directly to about 100 of the transitions to provide an experimentally derived surface for intramolecular vibrational energy redistribution (IVR) quantum dynamics calculations. Higher resolution stimulated emission pumping spectra from different vibrational levels in the {\~B} state reveal a complex progression from unfragmented/slightly Fermi-resonant states, to highly fragmented states above v1=8.",

author = "R. Bigwood and B. Milam and M. Gruebele",

note = "Funding Information: We thank Prof. C.B. Moore for enlightening discussions. This research was funded by an NYI grant from the NSF (CHE 94-57970) and a David and Lucile Packard Fellowship. MG also gratefully acknowledges a Fellowship from the Sloan Foundation. ",

year = "1998",

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doi = "10.1016/S0009-2614(98)00190-0",

language = "English (US)",

volume = "287",

pages = "333--341",

journal = "Chemical Physics Letters",

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TY - JOUR

T1 - The ground state vibrational structure of SCCl2

T2 - Observation of backbone IVR

AU - Bigwood, R.

AU - Milam, B.

AU - Gruebele, M.

N1 - Funding Information: We thank Prof. C.B. Moore for enlightening discussions. This research was funded by an NYI grant from the NSF (CHE 94-57970) and a David and Lucile Packard Fellowship. MG also gratefully acknowledges a Fellowship from the Sloan Foundation.

PY - 1998/5/1

Y1 - 1998/5/1

N2 - Vibrationally excited SCCl2 is a model system for energy redistribution among backbone vibrational modes. Over 200 transitions in the X̃←B̃ dispersed fluorescence spectrum of thiophosgene have been observed to map the ground electronic surface up to 15000 cm-1. An analytical six-dimensional potential surface derived from ab initio calculations has been fitted directly to about 100 of the transitions to provide an experimentally derived surface for intramolecular vibrational energy redistribution (IVR) quantum dynamics calculations. Higher resolution stimulated emission pumping spectra from different vibrational levels in the B̃ state reveal a complex progression from unfragmented/slightly Fermi-resonant states, to highly fragmented states above v1=8.

AB - Vibrationally excited SCCl2 is a model system for energy redistribution among backbone vibrational modes. Over 200 transitions in the X̃←B̃ dispersed fluorescence spectrum of thiophosgene have been observed to map the ground electronic surface up to 15000 cm-1. An analytical six-dimensional potential surface derived from ab initio calculations has been fitted directly to about 100 of the transitions to provide an experimentally derived surface for intramolecular vibrational energy redistribution (IVR) quantum dynamics calculations. Higher resolution stimulated emission pumping spectra from different vibrational levels in the B̃ state reveal a complex progression from unfragmented/slightly Fermi-resonant states, to highly fragmented states above v1=8.

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