B3LYP study of the dipole moment and the static dipole (hyper)polarizabilities of <i>para</i>‐nitroaniline in gas phase

Soscún, Humberto; Castellano, Olga; Bermúdez, Yaneth; Toro, Carlos; Cubillán, Néstor; Hinchliffe, Alan; Phu, Do Xuan

doi:10.1002/qua.20821

Cited by 18 publications

(9 citation statements)

References 26 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…[45][46][47][48][49][50][51] We optimized the geometry of the molecule in the C 2v symmetry. This geometry however results in a vibrational mode with an imaginary frequency with modulus 238 cm −1 , meaning it is actually a saddle point.…”

Section: Numerical Resultsmentioning

confidence: 99%

Stereoelectronic, Vibrational, and Environmental Contributions to Polarizabilities of Large Molecular Systems: A Feasible Anharmonic Protocol

Egidi

Giovannini

Piccardo

et al. 2014

J. Chem. Theory Comput.

View full text Add to dashboard Cite

Reliable computations of linear and non-linear optical properties of molecular systems in condensed phases require a proper account of stereo-electronic, vibrational, and environmental effects. In the framework of density functional theory, these effects can be accurately introduced using second-order vibrational perturbation theory in conjunction with polarizable continuum models. We illustrate the combination of an anharmonic description of the ground-state potential energy surface with solvation effects treated with the polarizable continuum model (PCM) in the calculation of the electronic, zero-point, and pure vibrational polarizabilities of selected systems. The description of the solvation environment is enriched by taking into account the dynamical aspects of the solute-solvent interactions through the inclusion of both electronic and vibrational non-equilbrium effects, as well as the direct effect of the solvent on the electric field that generates the molecular response (local field effect). This treatment yields accurate results which can be directly compared with experimental findings without the need of empirical corrections.

show abstract

Section: Numerical Resultsmentioning

confidence: 99%

Stereoelectronic, Vibrational, and Environmental Contributions to Polarizabilities of Large Molecular Systems: A Feasible Anharmonic Protocol

Egidi

Giovannini

Piccardo

et al. 2014

J. Chem. Theory Comput.

View full text Add to dashboard Cite

show abstract

“…8 Yang et al also concluded that ␤ of p-NA is nearly insensitive to the choice of a basis set, in contrast to the earlier findings, 2,3 which showed that augmentation of the basis set with both polarization and diffuse functions is necessary to obtain reliable values of NLO properties. At the same time, another study by Soscun et al 32 found that hyperpolarizability of p-NA do not significantly vary in the series of basis sets with both polarization and diffuse functions.…”

Section: Introductionmentioning

confidence: 85%

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

Suponitsky

Tafur

Masunov

2008

The Journal of Chemical Physics

161

125

View full text Add to dashboard Cite

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.

show abstract

“…In that study, four hybrid functionals were tested against CCSD using modest basis sets, and the conclusions were that the 6-31+G* basis is adequate at least for obtaining reasonable relative values of β, and that the most accurate values were obtained with the functional that is a metahybrid, BMK (9% larger than CCSD), followed closely by PBE0 (10%), while B97-2 and B3LYP yielded values that were too large by 16% and 22%, respectively. Soscun et al 9 studied pNA in the gas-phase with MP2 and B3LYP, reporting static β and γ values at the HF, MP2, and B3LYP levels of theory. The comparison to experiment is only qualitative since the experimental values are in solution and have been scaled to zero frequency using a two-state approximation.…”

Section: Introductionmentioning

confidence: 99%

Analysis of nonlinear optical properties in donor–acceptor materials

Day

Pachter

Nguyen

2014

The Journal of Chemical Physics

View full text Add to dashboard Cite

Time-dependent density functional theory has been used to calculate nonlinear optical (NLO) properties, including the first and second hyperpolarizabilities as well as the two-photon absorption cross-section, for the donor-acceptor molecules p-nitroaniline and dimethylamino nitrostilbene, and for respective materials attached to a gold dimer. The CAMB3LYP, B3LYP, PBE0, and PBE exchange-correlation functionals all had fair but variable performance when compared to higher-level theory and to experiment. The CAMB3LYP functional had the best performance on these compounds of the functionals tested. However, our comprehensive analysis has shown that quantitative prediction of hyperpolarizabilities is still a challenge, hampered by inadequate functionals, basis sets, and solvation models, requiring further experimental characterization. Attachment of the Au2S group to molecules already known for their relatively large NLO properties was found to further enhance the response. While our calculations show a modest enhancement for the first hyperpolarizability, the enhancement of the second hyperpolarizability is predicted to be more than an order of magnitude.

show abstract

B3LYP study of the dipole moment and the static dipole (hyper)polarizabilities of para‐nitroaniline in gas phase

Cited by 18 publications

References 26 publications

Stereoelectronic, Vibrational, and Environmental Contributions to Polarizabilities of Large Molecular Systems: A Feasible Anharmonic Protocol

Stereoelectronic, Vibrational, and Environmental Contributions to Polarizabilities of Large Molecular Systems: A Feasible Anharmonic Protocol

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

Analysis of nonlinear optical properties in donor–acceptor materials

Contact Info

Product

Resources

About