• Fiber optic networks– must be fast-acting– must integrate into fiber

systems– must operate at infrared

wavelengths

• Eye protection– scope sights– binoculars– must operate at both visible

and infrared wavelengths

ApplicationsOptical Limiters

Acquisition of spectroscopic and computational instruments for undergraduate education and research in nonlinear optical

materialsJames Butler, Pacific University, DMR 0521496

The optical limiters in this investigation use nonlinear absorbers. The percentage of light that these materials absorb increases with the intensity of the incident light.

Dim Light In Dim Light Out

Bright Light In Dim Light Out

Optical limiters are devices that can be used to control the brightness of the light that reaches a sensitive optical component

Optical Limiting in Capillary Waveguides at Infrared Wavelengths

1050nm Nonlinear Transmission

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Energy coupled into core (nJ)

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lativ

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Real

XS0=4e-20 XS2=9.8e-17 XSD=5e-45 R=3.8 ISC1=1e-6

• Simulations and inset images are consistent with the energy being confined to a small region within the core leading to an enhanced optical limiting response

• Simulations indicate that two-photon absorption plays a significant role in optical limiting for OsPZnOs in infrared

• Silica capillaries with 10 μm internal diameter filled with 0.2mM solution of OsPZnOs dissolved in DMSO

• Inset shows energy distribution (false color) within the capillary core (white circle)

* Experiments are continuing at Pacific University with equipment purchased from this grant

The data shown here was taken by the PI and collaborators at the Naval Research Laboratory (NRL) in the summer of 2006.* The modeling of the data was done by undergraduates at Pacific University in the summer of 2007.

1000nm Nonlinear Transmission

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XS0=4.59e-20 XS2=1e-16 XSD=2.5e-46 R=3.4 ISC1=1e-6

1000nm Nonlinear Transmission Data 1050nm Nonlinear Transmission Data

• = data• = simulation

• = data• = simulation

James Butler, Pacific University, DMR 0521496

Molecular Modeling Results

Undergraduate student, Joshua D. King, completed his senior thesis in chemistry titled, “Investigation of the electronic Spectroscopic Properties of Phthalocyanines and Related Dye Molecules Using Time-Dependent Density Functional Theory”.

SCIENTIFIC PROGRESS•Results to Date

• A computational study of the effect of macrocycle size and symmetry was undertaken for a series of Magnesium Phthalo- and Naphthalo-cyanines

• Simulated electronic absorption spectra for ground singlet, S0, first excited singlet, S1, and first excited Triplet states were calculated and are shown to the right.

• Ground state MO density is observed to be a orbital with electron density distributed equally on the thalocyanine plane. Excited singlet states are observed to concentrate MO density on a single axis of the molecule.

• When the two molecular axes are of the same length, the LUMO orbitals are degenerate. However, counter to expectations, for molecules with unequal length in the axes of the macrocycle plane, the lower energy virtual orbital concentrates MO density on the short axis. This is the origin of splitting in the ground state spectra.

SOFTWARE IMPLEMENTATION• Developed modeling protocol using the TD-DFT implementation in the ADF software

packageThe ADF implementation of TD-DFT with Slater type orbitals was found to be superior in predicting electronic spectra of both ground and excited states.The software also runs Parallel on our Power Macintosh, greatly improving computation times.

• Software License supported by internal Faculty Development Grant from Pacific University to co-Pi Johnson

Mixed Mg naphthalo- phthalo-cyaninesTD-DFT SAOP/TZ2P

Simulated Singlet and Triplet Spectra

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wavelength (nm)

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*S2 excited state

James Butler, Pacific University, DMR 0521496