TD-DFT calculations of one- and two-photon absorption in Coumarin C153 and Prodan: attuning theory to experiment

2017 ◽  
Vol 19 (42) ◽  
pp. 28824-28833 ◽  
Author(s):  
Merle Uudsemaa ◽  
Aleksander Trummal ◽  
Sophie de Reguardati ◽  
Patrik R. Callis ◽  
Aleksander Rebane
Keyword(s):  
Experimental Data ◽  
Dipole Moment ◽  
Dft Calculations ◽  
Electric Dipole ◽  
Photon Absorption ◽  
Two Photon Absorption ◽  
Two Photon ◽  
Permanent Electric Dipole Moment ◽  
Td Dft ◽  
Accurate Experimental Data

TD-DFT calculations of two-photon absorption (2PA) and the permanent electric dipole moment change (Δμ) of C153 and Prodan in toluene and DMSO are benchmarked relative to accurate experimental data to reveal the best performing methods.

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.

scholarly journals Solute-solvent electronic interaction is responsible for initial charge separation in ruthenium complexes [Ru(bpy)3]2+ and [Ru(phen)3]2+

2019 ◽  
Vol 2 (1) ◽  
Author(s):  
Charles W. Stark ◽  
Aleksander Trummal ◽  
Merle Uudsemaa ◽  
Juri Pahapill ◽  
Matt Rammo ◽  
...  
Keyword(s):  
Dipole Moment ◽  
Charge Separation ◽  
Photon Absorption ◽  
Electronic Interaction ◽  
Two Photon Absorption ◽  
Two Photon ◽  
Permanent Electric Dipole Moment ◽  
Initial Charge ◽  
Solvent Molecules ◽  
Solvent Clusters

Abstract Origin of the initial charge separation in optically-excited Ruthenium(II) tris(bidentate) complexes of intrinsic D3 symmetry has remained a disputed issue for decades. Here we measure the femtosecond two-photon absorption (2PA) cross section spectra of [Ru(2,2′-bipyridine)3]2 and [Ru(1,10-phenanthroline)3]2 in a series of solvents with varying polarity and show that for vertical transitions to the lower-energy 1MLCT excited state, the permanent electric dipole moment change is nearly solvent-independent, Δμ = 5.1–6.3 D and 5.3–5.9 D, respectively. Comparison of experimental results with quantum-chemical calculations of complexes in the gas phase, in a polarizable dielectric continuum and in solute-solvent clusters containing up to 18 explicit solvent molecules indicate that the non-vanishing permanent dipole moment change in the nominally double-degenerate E-symmetry state is caused by the solute-solvent interaction twisting the two constituent dipoles out of their original opposite orientation, with average angles matching the experimental two-photon polarization ratio.

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.

Prediction of two-photon absorption enhancement in red fluorescent protein chromophores made from non-canonical amino acids

2016 ◽  
Vol 18 (35) ◽  
pp. 24408-24416 ◽  
Author(s):  
M. Alaraby Salem ◽  
Isaac Twelves ◽  
Alex Brown
Keyword(s):  
Amino Acids ◽  
Fluorescent Protein ◽  
Photon Absorption ◽  
Absorption Enhancement ◽  
Red Fluorescent Protein ◽  
Two Photon Absorption ◽  
Two Photon ◽  
Td Dft

TD-DFT screening of RFP-derived chromophores using B3LYP and CAM-B3LYP highlights a Gold FP-like chromophore with large TPA (two-photon absorption).

scholarly journals Two-photon absorption of fluorescent protein chromophores incorporating non-canonical amino acids: TD-DFT screening and classical dynamics

2015 ◽  
Vol 17 (38) ◽  
pp. 25563-25571 ◽  
Author(s):  
M. Alaraby Salem ◽  
Alex Brown
Keyword(s):  
Amino Acids ◽  
Fluorescent Protein ◽  
Md Simulations ◽  
Nitro Derivative ◽  
Photon Absorption ◽  
Classical Dynamics ◽  
Two Photon Absorption ◽  
Two Photon ◽  
Td Dft

TD-DFT screening of unnatural GFP-like chromophores highlights a nitro-derivative with large TPA (two-photon absorption) that is further studied in a protein enclosure by MD simulations.

Two-photon absorption of styryl-quinolinium, -pyridinium, and -barbituric acid derivatives, and intramolecular charge transfer

2001 ◽  
Vol 79 (2) ◽  
pp. 174-182 ◽  
Author(s):  
XiaoMei Wang ◽  
Chun Wang ◽  
WenTao Yu ◽  
YuFang Zhou ◽  
Xian Zhao ◽  
...  
Keyword(s):  
Dipole Moment ◽  
Charge Transfer ◽  
Barbituric Acid ◽  
Intramolecular Charge Transfer ◽  
Theoretical Calculations ◽  
Photon Absorption ◽  
Amino Groups ◽  
Element Analysis ◽  
Two Photon Absorption ◽  
Two Photon

A series of new chromophores, styryl-parent end-capped with various donors, and with barbituric acid, methyl-pyridinium, and methyl-quinolinium as the acceptors, have been synthesized and characterized by element analysis or X-ray diffraction. Using the Z-scan system, their two-photon absorption (TPA) cross-section values (δ) have been determined under excitation with 10 Hz, and 1064 nm, 35 ps mode-locked Nd:YAG laser pulse in DMF with do= 0.05 M. The effective δ value is as high as 10.9 × 10–48 cm4 s per photon for trans-4-(4'-N,N-diphenyl amino) styryl-N-methyl quinolinium iodide (DPASQI). The δ value increases from barbituric acid- to pyridinium- to quinolinium-derivatives apparently due to the increase in both the conjugated degree and planarity; however, when the acceptor is fixed, the δ value increases from dialkyl amino groups to diphenyl amino groups even though the latter is a weaker donor than the dialkyl amino groups. Theoretical calculations confirm that the increased distortion from planarity for the barbituric acid derivative makes its δ value decrease. The relatively large δ value for quinolinium- or pyridinium-derivatives originates from larger intramolecular charge transfer, which can be characterized by the difference of dipole moment (Δµge) between the S0 and S1, and the transition dipole moment (Mee') between S1 and S2.Key words: two-photon absorption, intramolecular charge transfer, styryl-quinolinium, styryl-pyridinium, styryl-barbituric acid.

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