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.
Molecular response properties from explicitly time-dependent configuration interaction methods
Rent:
Rent this article for
USD
10.1063/1.2749503
/content/aip/journal/jcp/127/3/10.1063/1.2749503
http://aip.metastore.ingenta.com/content/aip/journal/jcp/127/3/10.1063/1.2749503

Figures

Image of FIG. 1.
FIG. 1.

In the upper panels shown are the dipole moments as a function of the time and the field amplitude for an excitation with “long” [, (a1)] and “short” [, (b1)] pulses. The lower panels [(a2) and (b2)] show the corresponding populations in various electronic states once the pulse is off. The TD-CISD method was employed with the aug-cc-pVDZ basis set and the laser frequency is chosen resonant with the transition.

Image of FIG. 2.
FIG. 2.

Shown are the Kennlinien, over , due to stimulation of with pulses with different carrier frequencies (0.10, 0.20, 0.30, 0.40, and 0.44 , steeper lines correspond to larger frequencies). The TD-CISD/aug-cc-pVQZ calculations are done with and .

Image of FIG. 3.
FIG. 3.

Shown are the dynamic polarizabilities of obtained from TD-CIS, TD-CIS(D), and TD-CISD calculations with the aug-cc-pVQZ basis set. The -shaped laser pulse [Eq. (13)] has a maximum amplitude and a width . Shown in the inset are the dynamic polarizabilities in comparison to variational calculations using different representations for the wave functions, as cited in Ref. 52: , , , and .

Image of FIG. 4.
FIG. 4.

Demonstrated is the harmonic generation for the different TD-CI methods. The frequency-dependent dipole moment squared is plotted on a logarithmic scale. The fundamental peak and the third and fifth harmonics are shown (nonlogarithmic and magnified) as insets. The TD-CIS, TD-CIS(D), and TD-CISD signals are calculated with the aug-cc-pVDZ basis set. The incident laser has a frequency of , a maximum field amplitude of , and a width .

Image of FIG. 5.
FIG. 5.

Shown is the frequency-dependent dipole moment squared, , for the three TD-CI methods on a logarithmic scale. The calculations are done with the aug-cc-pVDZ basis set and the laser parameters are chosen to be , , .

Image of FIG. 6.
FIG. 6.

Shown are the areas under the harmonic signals as a function of the maximum field amplitude calculated with the TD-CISD method. Solid line, area of the fundamental peak (1HG); dashed line, area of the second harmonic (SHG) peak (amplified by a factor of 1000); dotted line, area of the third harmonic (THG) peak (amplified by a factor of 50 000). The laser parameters are as follows: polarized, shaped, , and . Shown in the subfigures are the peak areas as a function of , , and , respectively.

Tables

Generic image for table
Table I.

Shown are the components of the transition dipole moments of together with the corresponding excitation energies calculated by the CISD method with the different basis sets ( and ). Independent calculations of the excitation energies with the ACES2 program give, for the basis sets, perfect agreement for , T, and Q, while for a small discrepancy to our calculation (of about ) exists, for reasons which are not clear (Ref. 64). All values are given in atomic units ( or ).

Generic image for table
Table II.

Listed are the quasistatic diagonal polarizability components of in comparison with experimental and other theoretical values. All values given are in .

Generic image for table
Table III.

Listed are the calculated diagonal polarizability elements in comparison to experimental data. All TD-CI calculations are done with the aug-cc-pVDZ basis set. All values are determined at the same frequency of and given in . ( could not be determined more accurately.)

Loading

Article metrics loading...

/content/aip/journal/jcp/127/3/10.1063/1.2749503
2007-07-17
2014-04-18
Loading

Full text loading...

This is a required field
Please enter a valid email address
752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Molecular response properties from explicitly time-dependent configuration interaction methods
http://aip.metastore.ingenta.com/content/aip/journal/jcp/127/3/10.1063/1.2749503
10.1063/1.2749503
SEARCH_EXPAND_ITEM