Predictions of Two Photon Absorption Profiles Using Time-Dependent Density Functional Theory Combined with SOS and CEO Formalisms

Tafur, Sergio; Михайлов, И. В.; Belfield, Kevin D.; Masunov, Artëm E.

doi:10.1007/978-3-642-01973-9_20

Cited by 3 publications

(6 citation statements)

References 36 publications

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“…The SOS method was utilized for calculation of hyperpolarizabilities ͑static and dynamic͒ at TDHF and TDDFT levels using the in-house FORTRAN code NLO. 52 State-to-state and permanent excited state dipoles that are input to NLO, were calculated in the a posteriori Tamm-Dancoff approximation, implemented in the locally modified version of GAUSSIAN 2003. 46 Availability of reliable experimental values of the gasphase hyperpolarizability of p-NA allows a direct comparison with our calculated data.…”

Section: Computational Detailsmentioning

confidence: 99%

Applicability of hybrid density functional theory methods to calculation of molecular hyperpolarizability

Suponitsky

Tafur

Masunov

2008

The Journal of Chemical Physics

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160

125

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The donor/acceptor (D/A) substituted pi-conjugated organic molecules possess extremely fast nonlinear optical (NLO) response time that is purely electronic in origin. This makes them promising candidates for optoelectronic applications. In the present study, we utilized four hybrid density functionals (B3LYP, B97-2, PBE0, BMK), Hartree-Fock, and second order Moller-Plesset correlation energy correction, truncated at second-order (MP2) methods with different basis sets to estimate molecular first hyperpolarizability (beta) of D/A-substituted benzenes and stilbenes (D=OMe, OH, NMe(2), NH(2); A=NO(2), CN). The results of density functional theory (DFT) calculations are compared to those of MP2 method and to the experimental data. We addressed the following questions: (1) the accurate techniques to compare calculated results to each other and to experiment, (2) the choice of the basis set, (3) the effect of molecular planarity, and (4) the choice of the method. Comparison of the absolute values of hyperpolarizabilities obtained computationally and experimentally is complicated by the ambiguities in conventions and reference values used by different experimental groups. A much more tangible way is to compare the ratios of beta's for two (or more) given molecules of interest that were calculated at the same level of theory and measured at the same laboratory using the same conventions and reference values. Coincidentally, it is the relative hyperpolarizabilities rather than absolute ones that are of importance in the rational molecular design of effective NLO materials. This design includes prediction of the most promising candidates from particular homologous series, which are to be synthesized and used for further investigation. In order to accomplish this goal, semiquantitative level of accuracy is usually sufficient. Augmentation of the basis set with polarization and diffuse functions changes beta by 20%; however, further extension of the basis set does not have significant effect. Thus, we recommend 6-31+G(*) basis set. We also show that the use of planar geometry constraints for the molecules, which can somewhat deviate from planarity in the gas phase, leads to sufficient accuracy (with an error less than 10%) of predicted values. For all the molecules studied, MP2 values are in better agreement with experiment, while DFT hybrid methods overestimate beta values. BMK functional gives the best agreement with experiment, with systematic overestimation close to the factor of 1.4. We propose to use the scaled BMK results for prediction of molecular hyperpolarizability at semiquantitative level of accuracy.

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Section: Computational Detailsmentioning

confidence: 99%

Applicability of hybrid density functional theory methods to calculation of molecular hyperpolarizability

Suponitsky

Tafur

Masunov

2008

The Journal of Chemical Physics

Self Cite

160

125

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“…In this Subsection we review the recent prediction of 2PA cross-sections published recently [138]. The conjugated chromophores selected in that study to illustrate the accuracy of ATDA method, are presented in Scheme 3.…”

Section: A1 (1)mentioning

confidence: 99%

“…We present 2PA resonant energies and cross-sections in Table 3 [138]. Figure 3 represents canonical orbitals, transition dipoles and excitation energies for compound 1a.…”

Section: A1 (1)mentioning

confidence: 99%

“…Overall, agreement with experiment validates the use of TD-DFT as a part of rational design strategies directed toward new and improved two-photon absorbing materials. We reviewed theoretical study [138] of five conjugated chromophores experimentally shown to have large two photon absorption cross-sections. The use of the third order response formalism within TD-DFT to calculate the frequency-dependent second order hyperpolarizability in both SOS and CEO methods to describe 2PA cross-sections resulted in very similar numerical values.…”

Section: A1 (1)mentioning

confidence: 99%

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Theory and computations of two-photon absorbing photochromic chromophores

Masunov

Михайлов

2010

Eur. J. Chem.

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KEYWORDSExponential growth in information technology generates ever increasing amounts of data, making recording density of the storage media crucially important. Two-photon absorption was proposed as a basis for high-density multi-layer technology for optical memory and logic devices. This technology suggests to use polymers, doped with photochromic compounds that undergo a reversible photoinduced isomerization, or photoswitching. In this review we consider recent theoretical works and benchmarking studies of the DFT-based methods, capable to predict two-photon absorption (2PA) and photochemical activity, Next we review the applications of these methods to design a prototype molecule that combines the photonmode recording property of photochromic compounds with large 2PA cross-section. We conclude that a posteriori Tamm-Dancoff approximation to the second order CEO approach in Density Functional Theory is the powerful tool for both quantitative predictions and qualitative understanding of the excited state processes in photophysics and photochemistry. We also emphasize general principles for the rational design of a two-photon operated photoswitch.TDDFT Organic photochemistry Photocyclization Photoinduced reactions Two-photon absorption State-to-state transition dipoles

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“…The accuracy of 2PA spectra predicted with this approximation compared favorably with both experiment 15,41−49 and exact third-order CEO predictions. 43 In this work we report the results of more systematic comparisons along these lines.…”

Section: Introductionmentioning

confidence: 98%

Comparison of TD-DFT Methods for the Calculation of Two-Photon Absorption Spectra of Oligophenylvinylenes

2013

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We investigate the accuracy of different formalisms within density functional theory in prediction of two-photon absorption (2PA) spectra for substituted oligophenylvinylenes compared to the experimental measurements. The quadratic response methods are compared with the recently proposed a posteriori Tamm−Dancoff approximation (ATDA) and previously published third-order coupled electronic oscillator results. Quadratic response is found to overestimate the cross sections in all cases. We trace the reasons to unreliable excited state description above the ionization threshold. In addition, quadratic response lacks the double excitations so that their contributions to the 2PA spectra are redistributed over the nearest single character excitations. This distorts the individual contributions to the 2PA response and affects the overall picture. For this reason, we do not recommend quadratic response for the essential state analysis, while ATDA can be used both for the 2PA predictions and the structure/property correlations. As an illustration for ATDA based essential state analysis, we report the mechanism of large 2PA in symmetric donor/acceptor substituted polyphenylvinylene (PPV) oligomers. While HOMO−LUMO transition provides the only bright intermediate state, the brightness of the one-photon absorption (1PA) to 2PA transition is associated with symmetric to asymmetric linear combination of the respective donor (HOMO − 1 to HOMO) or acceptor (LUMO to LUMO + 1) fragment orbitals of the donor or acceptor substituents. We also study the effect of the fraction of Hartree−Fock (HF) exchange on 2PA excitation energies and cross sections. Higher exchange (BMK and M05-2X) and range separated (CAM-B3LYP) hybrid functionals are found to yield rather inaccurate predictions both quantitatively and qualitatively. The results obtained with the long-range corrected functional LC-BLYP do not seem to be useful at all. This failure of the exchange-correlation functionals with the correct asymptotic is traced to inaccurate transition dipoles between the valence states, where only functionals with lower HF exchange succeed. A new sum over states (SOS) cutoff procedure is proposed to compensate for the collapse of the higher-lying excited states obtained with the hybrid functionals.

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Predictions of Two Photon Absorption Profiles Using Time-Dependent Density Functional Theory Combined with SOS and CEO Formalisms

Cited by 3 publications

References 36 publications

Applicability of hybrid density functional theory methods to calculation of molecular hyperpolarizability

Applicability of hybrid density functional theory methods to calculation of molecular hyperpolarizability

Theory and computations of two-photon absorbing photochromic chromophores

Comparison of TD-DFT Methods for the Calculation of Two-Photon Absorption Spectra of Oligophenylvinylenes

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