S0-S0 spectroscopy of the van der waals complexes of azulene with rare gases

Osama K. Abou-Zied, Hemant K. Sinha, Ronald P. Steer

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

The S2-S0 fluorescence emission and excitation spectra of jet-cooled azulene and its complexes with the rare gases, Ne, Ar, Kr, and Xe, have been measured. Features due to AZ-RG (n = 1-4 when RG = Ar, Kr, Xe and n = 1 when RG = Ne) are observed in the 82-80 fluorescence excitation spectra when azulene is coexpanded with the rare gases. The microscopic solvent shifts, ôï>, of the origin bands for each complex scale linearly with the polarizability of the adatom(s), indicating that binding is dominated by dispersive interactions. This conclusion has been confirmed in calculations of the separate contributions of dispersion and induction to op. Mildly anharmonic progressions in very low frequency excited-state intermolecular (van der Waals) modes are attached to the origin bands of each AZ-Krn and AZ-Xen complex. The dominant progression is assigned to single quantum changes in that excited-state bending mode which involves motion of the adatom(s) in the plane perpendicular to the azulene ring containing the long (x) axis of the molecule. This assignment has been confirmed by calculating the frequencies of the bending and stretching vibrations in the ground state by using one-dimensional Morse and Taylor's series potential functions. The most stable geometries of the n = 1-4 complexes in their ground states have been calculated by using a summation of pairwise atom-atom Lennard-Jones 6-12 potentials. The potential minima of the 1:1 complexes are located over the seven-membered ring; no second minimum is found over the five-membered ring. The most stable 1:2 species appears to be the symmetric (1 + 1) complex in which one adatom is bound on each side of the azulene surface. Some evidence of the asymmetric (2 + 0) isomer is also found.

Original languageEnglish
Pages (from-to)4375-4381
Number of pages7
JournalJournal of Physical Chemistry
Volume100
Issue number11
Publication statusPublished - 1996

Fingerprint

azulene
Noble Gases
Adatoms
Inert gases
rare gases
Spectroscopy
adatoms
Excited states
Ground state
Fluorescence
progressions
spectroscopy
excitation
rings
Atoms
Taylor series
Isomers
fluorescence
Stretching
bending vibration

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

S0-S0 spectroscopy of the van der waals complexes of azulene with rare gases. / Abou-Zied, Osama K.; Sinha, Hemant K.; Steer, Ronald P.

In: Journal of Physical Chemistry, Vol. 100, No. 11, 1996, p. 4375-4381.

Research output: Contribution to journalArticle

Abou-Zied, Osama K. ; Sinha, Hemant K. ; Steer, Ronald P. / S0-S0 spectroscopy of the van der waals complexes of azulene with rare gases. In: Journal of Physical Chemistry. 1996 ; Vol. 100, No. 11. pp. 4375-4381.
@article{04ee03730e3942c99890950f38523bc2,
title = "S0-S0 spectroscopy of the van der waals complexes of azulene with rare gases",
abstract = "The S2-S0 fluorescence emission and excitation spectra of jet-cooled azulene and its complexes with the rare gases, Ne, Ar, Kr, and Xe, have been measured. Features due to AZ-RG (n = 1-4 when RG = Ar, Kr, Xe and n = 1 when RG = Ne) are observed in the 82-80 fluorescence excitation spectra when azulene is coexpanded with the rare gases. The microscopic solvent shifts, {\^o}{\"i}>, of the origin bands for each complex scale linearly with the polarizability of the adatom(s), indicating that binding is dominated by dispersive interactions. This conclusion has been confirmed in calculations of the separate contributions of dispersion and induction to op. Mildly anharmonic progressions in very low frequency excited-state intermolecular (van der Waals) modes are attached to the origin bands of each AZ-Krn and AZ-Xen complex. The dominant progression is assigned to single quantum changes in that excited-state bending mode which involves motion of the adatom(s) in the plane perpendicular to the azulene ring containing the long (x) axis of the molecule. This assignment has been confirmed by calculating the frequencies of the bending and stretching vibrations in the ground state by using one-dimensional Morse and Taylor's series potential functions. The most stable geometries of the n = 1-4 complexes in their ground states have been calculated by using a summation of pairwise atom-atom Lennard-Jones 6-12 potentials. The potential minima of the 1:1 complexes are located over the seven-membered ring; no second minimum is found over the five-membered ring. The most stable 1:2 species appears to be the symmetric (1 + 1) complex in which one adatom is bound on each side of the azulene surface. Some evidence of the asymmetric (2 + 0) isomer is also found.",
author = "Abou-Zied, {Osama K.} and Sinha, {Hemant K.} and Steer, {Ronald P.}",
year = "1996",
language = "English",
volume = "100",
pages = "4375--4381",
journal = "Journal of Physical Chemistry",
issn = "0022-3654",
publisher = "American Chemical Society",
number = "11",

}

TY - JOUR

T1 - S0-S0 spectroscopy of the van der waals complexes of azulene with rare gases

AU - Abou-Zied, Osama K.

AU - Sinha, Hemant K.

AU - Steer, Ronald P.

PY - 1996

Y1 - 1996

N2 - The S2-S0 fluorescence emission and excitation spectra of jet-cooled azulene and its complexes with the rare gases, Ne, Ar, Kr, and Xe, have been measured. Features due to AZ-RG (n = 1-4 when RG = Ar, Kr, Xe and n = 1 when RG = Ne) are observed in the 82-80 fluorescence excitation spectra when azulene is coexpanded with the rare gases. The microscopic solvent shifts, ôï>, of the origin bands for each complex scale linearly with the polarizability of the adatom(s), indicating that binding is dominated by dispersive interactions. This conclusion has been confirmed in calculations of the separate contributions of dispersion and induction to op. Mildly anharmonic progressions in very low frequency excited-state intermolecular (van der Waals) modes are attached to the origin bands of each AZ-Krn and AZ-Xen complex. The dominant progression is assigned to single quantum changes in that excited-state bending mode which involves motion of the adatom(s) in the plane perpendicular to the azulene ring containing the long (x) axis of the molecule. This assignment has been confirmed by calculating the frequencies of the bending and stretching vibrations in the ground state by using one-dimensional Morse and Taylor's series potential functions. The most stable geometries of the n = 1-4 complexes in their ground states have been calculated by using a summation of pairwise atom-atom Lennard-Jones 6-12 potentials. The potential minima of the 1:1 complexes are located over the seven-membered ring; no second minimum is found over the five-membered ring. The most stable 1:2 species appears to be the symmetric (1 + 1) complex in which one adatom is bound on each side of the azulene surface. Some evidence of the asymmetric (2 + 0) isomer is also found.

AB - The S2-S0 fluorescence emission and excitation spectra of jet-cooled azulene and its complexes with the rare gases, Ne, Ar, Kr, and Xe, have been measured. Features due to AZ-RG (n = 1-4 when RG = Ar, Kr, Xe and n = 1 when RG = Ne) are observed in the 82-80 fluorescence excitation spectra when azulene is coexpanded with the rare gases. The microscopic solvent shifts, ôï>, of the origin bands for each complex scale linearly with the polarizability of the adatom(s), indicating that binding is dominated by dispersive interactions. This conclusion has been confirmed in calculations of the separate contributions of dispersion and induction to op. Mildly anharmonic progressions in very low frequency excited-state intermolecular (van der Waals) modes are attached to the origin bands of each AZ-Krn and AZ-Xen complex. The dominant progression is assigned to single quantum changes in that excited-state bending mode which involves motion of the adatom(s) in the plane perpendicular to the azulene ring containing the long (x) axis of the molecule. This assignment has been confirmed by calculating the frequencies of the bending and stretching vibrations in the ground state by using one-dimensional Morse and Taylor's series potential functions. The most stable geometries of the n = 1-4 complexes in their ground states have been calculated by using a summation of pairwise atom-atom Lennard-Jones 6-12 potentials. The potential minima of the 1:1 complexes are located over the seven-membered ring; no second minimum is found over the five-membered ring. The most stable 1:2 species appears to be the symmetric (1 + 1) complex in which one adatom is bound on each side of the azulene surface. Some evidence of the asymmetric (2 + 0) isomer is also found.

UR - http://www.scopus.com/inward/record.url?scp=0001265822&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0001265822&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0001265822

VL - 100

SP - 4375

EP - 4381

JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

SN - 0022-3654

IS - 11

ER -