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Resonant 2-photon ionization study of the conformation and the binding of water molecules to 2-phenylethanethiol
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10.1063/1.2903477
/content/aip/journal/jcp/128/16/10.1063/1.2903477
http://aip.metastore.ingenta.com/content/aip/journal/jcp/128/16/10.1063/1.2903477

Figures

Image of FIG. 1.
FIG. 1.

Molecular conformers of PET and their relative energies at the level. The conformers are labeled gauche/anti according to the arrangement of the side chain with respect to and gauche/trans in relation to (see Table I). Gg conformers are further distinguished by the label to indicate a structure permitting an interaction. Predicted TDM alignments for the transition are indicated by the double-headed arrows, while the dotted lines indicate the axis perpendicular to the substituent corresponding to .

Image of FIG. 2.
FIG. 2.

Molecular orbitals of PET conformer at level (computed for the third root, i.e., state) that were included in the active space. The labels indicate the original energy ordering at the level.

Image of FIG. 3.
FIG. 3.

(a) Energies of the excited state of EtSH from rigid potential energy scans at the EtSH level, using an active space of four sulfur-centered orbitals and four electrons. Changes in bond lengths are plotted relative to the optimized ground state values (, ). (b) vertical excitation energies for selected PET species, from and calculations. TD-DFT results are not presented; the excited states of water clusters show such strong mixing between states it is not possible to clearly identify them in usual terms.

Image of FIG. 4.
FIG. 4.

[(a) and (b)] One-color R2PI spectra of PET recorded in mass channels corresponding to and isotopomers. Traces (c) and (d) show the UV-UV holeburning spectra for the PET Ag and conformers, respectively, obtained by probing origin bands A at and G at of trace (a). Holeburn features are labeled with their shift relative to their origin band.

Image of FIG. 5.
FIG. 5.

R2PI experimental contours of origin bands A at (a) and G at (b), together with the predicted contours for all anti and gauche conformers. Simulation parameters are taken from Table I: ground state rotational constants from structures; percentage changes in rotational constants upon excitation , , from and calculations; and hybrid band character from single point calculations. (a) and half width at half height (b) and .

Image of FIG. 6.
FIG. 6.

Nomenclature, structures, and relative energies for PET water clusters at the level. Predicted TDM alignments for the transition are indicated by the double-headed arrows, while the dotted lines indicate the axis perpendicular to the substituent corresponding to .

Image of FIG. 7.
FIG. 7.

One-color R2PI spectra probing the mass channels of [(a) and (b)] and (c) for the isotopomer. Traces (d) and (e) show the UV-UV holeburning spectra for and conformers, respectively, obtained by probing origin bands 37 574 and of trace (b). and cluster peaks are labeled (▼) or , respectively. Holeburn features are labeled with their shift relative to their origin band. Except for (a), the time delay between valve opening and laser firing was set to optimize cluster formation.

Image of FIG. 8.
FIG. 8.

(a) One-color R2PI ion signal for PET species as a function of delay time between opening the pulse valve and firing the UV laser. (b) Two-color enhancement of ion signal as a function of delay time between the resonant and nonresonant laser pulses. Simulations are based on each laser having a temporal profile with Gaussian FWHM of and lifetimes of 0.5 or .

Image of FIG. 9.
FIG. 9.

R2PI experimental contours of origin bands at (a) and at (b), together with predicted contours for and all conformers. Simulation parameters are taken from Table III: ground state rotational constants from structures; percentage changes in rotational constants upon excitations , , from and calculations; and hybrid band character from single point calculations. and .

Tables

Generic image for table
Table I.

The ab initio calculated molecular properties of PET monomers.

Generic image for table
Table II.

Vibrational assignments for the R2PI spectrum of PET.

Generic image for table
Table III.

Ab initio calculated molecular properties of the Ag and PET hydrate clusters.

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/content/aip/journal/jcp/128/16/10.1063/1.2903477
2008-04-22
2014-04-18
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Resonant 2-photon ionization study of the conformation and the binding of water molecules to 2-phenylethanethiol (PhCH2CH2SH)
http://aip.metastore.ingenta.com/content/aip/journal/jcp/128/16/10.1063/1.2903477
10.1063/1.2903477
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