1887
banner image
No data available.
Please log in to see this content.
You have no subscription access to this content.
No metrics data to plot.
The attempt to load metrics for this article has failed.
The attempt to plot a graph for these metrics has failed.
Conformation-resolved UV spectra of Pb(II) complexes: A gas phase study of the sandwich structures [Pb(toluene)2]2+ and [Pb(benzene)2]2+
Rent:
Rent this article for
USD
10.1063/1.4801440
/content/aip/journal/jcp/138/16/10.1063/1.4801440
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/16/10.1063/1.4801440

Figures

Image of FIG. 1.
FIG. 1.

Example of a photofragment mass spectrum for [Pb(benzene)2]2+ recorded after trapping and irradiation at 45 355 cm−1. Also shown is the structure calculated for this ion.

Image of FIG. 2.
FIG. 2.

UV photofragment spectrum recorded for [Pb(benzene)2]2+ overlaid with electronic excitations where the energies and oscillator strengths have been calculated using TDDFT (CAM-B3LYP/6-311++G(d,p)[SDD] at BVP86 geometry). The calculated transitions are shown as vertical lines and are for two conformers (C2 and C2v ) of [Pb(benzene)2]2+; however, on the scale of the plot the individual transitions are not resolved.

Image of FIG. 3.
FIG. 3.

Example of a photofragmentation mass spectrum for [Pb(toluene)2]2+ recorded after trapping and irradiation at 42 135 cm−1. Also shown are the three separate conformations of [Pb(toluene)2]2+ which calculations suggest may be present in the experiment.

Image of FIG. 4.
FIG. 4.

UV photofragment spectrum recorded for [Pb(toluene)2]2+ overlaid with electronic excitations where the energies and oscillator strengths have been calculated using TDDFT (CAM-B3LYP/6-311++G(d,p)[SDD] at BVP86 geometry). Results calculated for the three separate conformations of [Pb(toluene)2]2+ are shown as vertical lines.

Image of FIG. 5.
FIG. 5.

Configurations involved in the dominant electronic excitation of C2v [Pb(benzene)2]2+. This ligand-to-metal (π → 6p) charge transfer transition is representative of other LMCT transitions. The lead atom is depicted at the centre of the structure as a grey sphere.

Image of FIG. 6.
FIG. 6.

UV photofragment spectrum recorded for [Pb(benzene)2]2+ overlaid with electronic excitations calculated for [Pb(benzene)]+ using TDDFT (CAM-B3LYP/6-311++G(d,p)[SDD] at BVP86 geometry). The calculated results are shown as vertical lines. The transitions identified by * are subject to spin contamination.

Image of FIG. 7.
FIG. 7.

UV photofragment spectrum recorded for [Pb(toluene)2]2+ overlaid with electronic excitations calculated for [Pb(toluene)]+ using TDDFT (CAM-B3LYP/6-311++G(d,p)[SDD] at BVP86 geometry). The calculated results are shown as vertical lines and note that the scales are the same as those used in Figure 4 . The transitions identified by * are subject to spin contamination.

Image of FIG. 8.
FIG. 8.

The types of excitation arising from a doublet ground state, where i represents a doubly occupied orbital, s represents the singly occupied orbital, and a represents an unoccupied orbital. The presence or absence of a bar over i, s or a indicates a beta or alpha spin electron, respectively.

Image of FIG. 9.
FIG. 9.

Analysis of the TDDFT excitations arising from the [Pb(benzene)]+ complex.

Tables

Generic image for table
Table I.

Binding energies for the [Pb(benzene)2]2+ complex with respect to various loss products and calculated using both BVP86/6-311++G(d,p)[SDD] and TPSSh/6-311++G(d,p)[SDD].

Generic image for table
Table II.

Binding energies for the [Pb(toluene)2]2+ complex with respect to various loss products and calculated using both BVP86/6-311++G(d,p)[SDD] and TPSSh/6-311++G(d,p)[SDD].

Generic image for table
Table III.

Summary of calculated TDDFT electronic transitions and their intensities (f ≥ 0.01) for [Pb(benzene)2]2+ and [Pb(benzene)]2+. The weight and character of the dominant configurations and the % Pb character are also given.

Generic image for table
Table IV.

Summary of the observed peak positions and the calculated TDDFT (CAM-B3LYP/6-311++G(d,p)[SDD] at BVP86 geometry) electronic transitions and oscillator strengths (f ≥ 0.01 in the experimental range 35 000–45 000 cm−1) for [Pb(benzene)]+. The weight and character of the dominant configuration for each spin and the % Pb character are also given as are values, which should be 0.75 in the absence of contamination.

Generic image for table
Table V.

Summary of the observed peak positions and the calculated TDDFT (CAM-B3LYP/6-311++G(d,p)[SDD] at BVP86 geometry) electronic transitions and oscillator strengths (f ≥ 0.01 in the experimental range 35 000–45 000 cm−1) for [Pb(toluene)2]2+. The weight and character of the two most dominant configurations and % Pb character are also given. Dominant transitions from both theory and experiment, are shown in bold.

Generic image for table
Table VI.

Summary of the observed peak positions and the calculated TDDFT (CAM-B3LYP/6-311++G(d,p)[SDD] at BVP86 geometry) electronic transitions and oscillator strengths (f ≥ 0.01 in the experimental range 35 000–45 000 cm−1) for [Pb(toluene)]+. The weight and character of the dominant configuration for each spin and the % Pb character are also given as are values, which should be 0.75 in the absence of contamination. The most dominant transitions, from theory or experiment, are shown in bold.

Generic image for table
Table VII.

The excited state spin contamination in each of the [Pb(X)]+ excited states, calculated assuming that all spin contamination comes from the next highest allowed spin component. Heavily spin contaminated states are shown in bold.

Loading

Article metrics loading...

/content/aip/journal/jcp/138/16/10.1063/1.4801440
2013-04-22
2014-04-18
Loading

Full text loading...

This is a required field
Please enter a valid email address
752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Conformation-resolved UV spectra of Pb(II) complexes: A gas phase study of the sandwich structures [Pb(toluene)2]2+ and [Pb(benzene)2]2+
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/16/10.1063/1.4801440
10.1063/1.4801440
SEARCH_EXPAND_ITEM