Theoretical studies on the one- and two-photon absorption of tetrabenzoporphyrins and phthalocyanines

2004 ◽  
Vol 82 (1) ◽  
pp. 19-26 ◽  
Author(s):  
Xin Zhou ◽  
Ai-Min Ren ◽  
Ji-Kang Feng ◽  
Xiao-Juan Liu
Keyword(s):  
Dipole Moment ◽  
Cross Sections ◽  
Density Functional ◽  
Transition Dipole Moment ◽  
Photon Absorption ◽  
Transition Dipole ◽  
Two Photon Absorption ◽  
Two Photon ◽  
Order Of Magnitude ◽  
The One

The one-photon absorption (OPA) properties of tetrabenzoporphyrins (TBPs) and phthalocyanines (Pcs) were studied using the semiempirical ZINDO method and time-dependent density functional theory (TDDFT), respectively. The compared results confirmed that the semiempirical ZINDO method was reasonably reliable when calculating the OPA of tetrabenzoporphyrins and phthalocyanines. On the basis of the OPA properties obtained from the ZINDO method, two-photon absorption (TPA) properties of two series of molecules were investigated, using ZINDO and sum-over-states (SOS) methods. The results showed that the TPA cross-sections of all molecules were in the range of 220.6 × 10–50 – 345.9 × 10–50 cm4·s·photon–1, which were in the same order of magnitude as the values reported in the literature. The relatively larger δ(ω) value for Pcs with respect to that for corresponding TBPs originates from larger intramolecular charge transfer, which can be characterized by the difference of dipole moment between S0 and S1 and the transition dipole moment between S1 and S5.Key words: two-photon absorption, ZINDO, sum-over-states, tetrabenzoporphyrin, phthalocyanines.

Studies on the two-photon absorption properties of trigonal dehydrobenzo[18]annulenes

2004 ◽  
Vol 82 (7) ◽  
pp. 1172-1178 ◽  
Author(s):  
Xin Zhou ◽  
Ai-Min Ren ◽  
Ji-Kang Feng ◽  
Xiao-Juan Liu
Keyword(s):  
Dipole Moment ◽  
Cross Section ◽  
Intermediate State ◽  
Density Functional ◽  
Transition Dipole Moment ◽  
Photon Absorption ◽  
Absorption Properties ◽  
Transition Dipole ◽  
Two Photon Absorption ◽  
Two Photon

The one-photon and two-photon absorption properties of donor–acceptor substituted dehydrobenzo[18]annulenes were determined by using density functional theory and ZINDO methods. The macrocycle containing C2v symmetry exhibited the largest TPA cross-section value of 3376 × 10–50 cm4 s/photon. The calculated results indicate that the TPA response in the whole molecule comes from the contribution of that in the every side in the trigon. It is notable that the magnitudes of the transition dipole moment from the virtual intermediate state to the TPA final state and the dipole moment difference between the ground state and the virtual intermediate state play important roles in increasing the TPA cross-section value. This series of molecules can circumvent the trade-off between efficiency and transparency, and they provide a promising direction for the further development of novel two-dimensional molecules with such properties.Key words: two-photon absorption, ZINDO, sum-over-states, dehydrobenzo[18] annulenes, transparency.

Spectral profiles of two-photon absorption: Coherent versus two-step two-photon absorption

2004 ◽  
Vol 846 ◽  
Author(s):  
S. Polyutov ◽  
I. Minkov ◽  
F. Gel'mukhanov ◽  
K. Kamada ◽  
A. Baev ◽  
...  
Keyword(s):  
Cross Sections ◽  
Degrees Of Freedom ◽  
Photon Absorption ◽  
Final State ◽  
Two Photon Absorption ◽  
Two Photon ◽  
Spectral Bands ◽  
Spectral Profiles ◽  
The One ◽  
Spectral Shapes

ABSTRACTWe present a theory of two-photon absorption in solutions which addresses the formation of spectral shapes taking account of the vibrational degrees of freedom. The theory is used to rationalize observed differences between spectral shapes of one- and two-photon absorption. We elaborate on two underlying causes, one trivial and one non-trivial, behind these differences. The first refers simply to the fact that the set of excited electronic states constituting the spectra will have different relative cross sections for one-and two- photon absorption. The second reason is that the two-step and coherent two-photon absorption processes are competing, making the one-and two-photon spectral bands different even considering a single final state. The theory is applied to the N-101 molecule [di-phenyl-amino-nitro-stilbene] which was recently studied experimentally in the paper [ T.-C. Lin, G.S. He, P.N. Prasad, and L.-S. Tan, J. Mater. Chem., 14, 982, 2004.]

Calculations of two-photon absorption cross sections by means of density-functional theory

2003 ◽  
Vol 374 (5-6) ◽  
pp. 446-452 ◽  
Author(s):  
Paweł Sałek ◽  
Olav Vahtras ◽  
Jingdong Guo ◽  
Yi Luo ◽  
Trygve Helgaker ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Cross Sections ◽  
Density Functional ◽  
Photon Absorption ◽  
Absorption Cross ◽  
Functional Theory ◽  
Two Photon Absorption ◽  
Two Photon

Soluble meso-tetrakis(arylethynyl)porphyrins — synthesis and optical properties

2014 ◽  
Vol 18 (10n11) ◽  
pp. 998-1013 ◽  
Author(s):  
Agnieszka Nowak-Król ◽  
Łukasz G. Łukasiewicz ◽  
Joy E. Haley ◽  
Mikhail Drobizhev ◽  
Aleksander Rebane ◽  
...  
Keyword(s):  
Optical Properties ◽  
Red Light ◽  
Photon Absorption ◽  
Two Photon Absorption ◽  
Two Photon ◽  
Resonance Enhancement ◽  
Order Of Magnitude ◽  
Homo And Lumo ◽  
The One ◽  
First Time

Trans- A 2 B 2-tetrakis(arylethynyl)porphyrins with suitable solubility in CH 2 Cl 2, CHCl 3, EtOAc , acetone and toluene have been obtained for the first time. Among two possible strategies the one comprising the synthesis of 5,15-dibromo-10,20-bis[(isopropylsilyl)ethynyl]porphyrin proved to be more efficient. The pathway towards densely substituted arylacetylenes has been optimized. The use of previously identified 3,4,5-trialkoxyaryl substituent was crucial for achieving the reasonable solubility. The optical properties of meso-substituted tetrakis(arylethynyl)porphyrins were studied showing that strong polarization imparted by direct conjugation of all four substituents with porphyrin core resulted not only in strong absorption of red light but also in a relatively long triplet lifetime. Meso-tetrakis(arylethynyl)porphyrins have a significantly longer lifetime of T1 state than bis(arylethynyl)porphyrins and in their case all the states are mixtures of transitions between the HOMO-1, HOMO and LUMO, LUMO+1 MOs. We show that the presence of two additional arylethynyl substituents at meso-positions enhance the maximum two-photon absorption cross-section of trans- A 2 B 2-tetrakis(arylethynyl)porphyrins by more than one order of magnitude. Maximum values as high as σ2 = 500 GM at 950 nm result from realization of suitable conditions for effective resonance enhancement along with a lowering of the energy and intensification of the two-photon allowed transitions in the Soret region.

Theoretical study of one- and two-photon absorption properties of olefin-linked paracyclophane oligomers

2006 ◽  
Vol 84 (9) ◽  
pp. 1114-1123 ◽  
Author(s):  
Xiang-Biao Zhang ◽  
Ji-Kang Feng ◽  
Ai-Min Ren ◽  
Chia-Chung Sun
Keyword(s):  
Cross Sections ◽  
Molecular Structures ◽  
Photon Absorption ◽  
Absorption Properties ◽  
Two Photon Absorption ◽  
Two Photon ◽  
Repeat Units ◽  
The One ◽  
Good Transparency ◽  
The Relationship

The electronic structures and the one- and two-photon absorption (TPA) properties of two series of the olefin-linked paracyclophane (pCp) oligomers have been studied using AM1 and ZINDO-SOS methods. The relationship between the TPA cross sections and the molecular chain length is obtained. The maximum TPA cross section increases in proportion to Nα (N denotes the number of repeat units) and the values of α depend on different molecular structures. The olefin-linked pCp oligomers, which have good transparency and large TPA cross sections, are promising candidates for TPA materials.Key words: two-photon properties, paracyclophane oligomer, AM1, ZINDO-SOS.

scholarly journals Theoretical modeling of two-photon absorption of benzoxazoles exhibiting excited state proton transfer

2018 ◽  
Vol 26 (2) ◽  
pp. 55-58
Author(s):  
Y. Syetov
Keyword(s):  
Absorption Spectra ◽  
Cross Section ◽  
Cross Sections ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Photon Absorption ◽  
Linear Absorption ◽  
Functional Theory ◽  
Two Photon Absorption ◽  
Two Photon

Two-photon absorption spectra of 2-(2'-hydroxyphenyl)benzoxazole, 2,5-bis(2-benzoxazolyl)phenol and 2,5-bis(2-benzoxazolyl)hydroquinone are modeled by time-dependent density functional theory calculations. In contrast to the linear absorption, where the transitions to the two lowest excited states are leading, the two-photon absorption cross sections are significant for the transitions to higher states which are weak in one-photon absorption spectra. The 2,5-bis(2-benzoxazolyl)phenol and 2,5-bis(2-benzoxazolyl)hydroquinone demonstrate the maximum cross section of about ten times larger than that of 2-(2'-hydroxyphenyl)benzoxazole. The largest value of the cross section is calculated for 2,5-bis(2-benzoxazolyl)hydroquinone to be about 1500 units of Goeppert-Mayer for excitation at 600 nm.

Ab Initio Design of Two-Photon Absorbing Materials

1999 ◽  
Vol 597 ◽  
Author(s):  
Paul N. Day ◽  
Kiet A. Nguyen ◽  
Ruth Pachter
Keyword(s):  
Excited State ◽  
Ab Initio ◽  
Nonlinear Optical ◽  
Dipole Moments ◽  
Transition Dipole Moment ◽  
Photon Absorption ◽  
Transition Dipole ◽  
Two Photon Absorption ◽  
Two Photon ◽  
Absorbing Materials

AbstractTwo-photon absorbing materials such as conjugated polyenes show promise as nonlinear optical materials. Prediction of two-photon absorption frequencies and cross-sections has been limited by the high level of ab initio calculations that must be carried out in order to accurately calculate excited state energies and transition dipole moments, by the size of many of the compounds of interest, and by the difficulty of handling condensed phase effects in the calculations. We have carried out geometry optimizations at the multi-configurational selfconsistent field level on a small polyene, hexatriene, both in the gas-phase and in solution, with the solvent effects being modeled by the effective fragment potential. The excited-state energies have been calculated by the multiconfigurational quasidegenerate perturbation theory. Transition dipole moment calculations have also been carried out, from which the two-photon absorption cross-section can be estimated. The results indicate that just one or two solvent molecules can have a large effect on the nonlinear optical properties of two-photon absorbing materials.

scholarly journals Multiphoton spectroscopy: An optical window into molecular electrostatics

2018 ◽  
Vol 190 ◽  
pp. 02009
Author(s):  
Aleksander Rebane
Keyword(s):  
Dipole Moment ◽  
Cross Sections ◽  
Electric Dipole ◽  
Stark Effect ◽  
Dipole Moments ◽  
Photon Absorption ◽  
Good Correspondence ◽  
Two Photon Absorption ◽  
Two Photon ◽  
All Optical

Quantitative knowledge about static molecular electric dipole moments is essential for understanding of intramolecular charge transfer as well as nanometer-scale static electric interactions. However, measuring or determining the molecular electrostatic properties with sufficient accuracy remains a challenging task. In our experiments, we measure the femtosecond two-photon absorption spectra- and cross sections of a range of organic- and organometallic chromophores in solution and use these data to determine the electric dipole moment change in corresponding lowest-energy dipole-allowed transition. Good correspondence of our experimental dipole moments with the quantum-chemical calculations as well as reports by other groups using conventional dipole moment measurement methods suggests that quantitative multiphoton spectroscopy may offer all-optical alternative to the traditional techniques such as Stark effect and electrochromism.

THEORETICAL STUDIES OF ONE- AND TWO-PHOTON ABSORPTION PROPERTIES FOR SYMMETRIC MOLECULES BASED ON BIS(STILBENE)DIETHYLENE

2006 ◽  
Vol 05 (03) ◽  
pp. 535-542 ◽  
Author(s):  
SHU-LAN ZHOU ◽  
XIAN ZHAO ◽  
XUE-QIN SUN ◽  
XIU-FENG CHENG
Keyword(s):  
Excited State ◽  
Cross Sections ◽  
Dipole Moments ◽  
Photon Absorption ◽  
Absorption Properties ◽  
Final State ◽  
Transition Dipole ◽  
Two Photon Absorption ◽  
Two Photon ◽  
Acceptor Side

In order to investigate the substituting effects on the two-photon absorption (TPA) cross-section and the position of the TPA peak, the one- and two-photon absorption properties of a series of symmetric molecules with bis(stilbene)diethylene π-conjugated bridge have been studied using ZINDO-SOS method. The transition moments from the ground state to the lowest excited state (M0k) and from the lowest excited state to the TPA final state (Mkn), together with the detuning energy ΔE = E0k - Ekn/2, were calculated using the INDO1 method included in the ZINDO program. The results indicate that bis-donor and bis-acceptor substitutions mainly affect the transition dipole moments M0k and Mkn, and that donor or acceptor side groups have a strong influence on the detuning energy. Meanwhile, it was found that the molecules with the bis-donor structure possess enhanced TPA cross sections, and the molecules with cyano or methoxy side groups have a large red-shift with respect to molecules without side groups.

Sign in / Sign up

Export Citation Format

Share Document