Search NASA⌕ Search

SEARCH · Search NASA

Results for “Hyperpolarizability”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Excited-State Dynamics and Nonlinear Optical Properties of Hyperpolarizable Chromophores Based on Conjugated Bis(terpyridyl)Ru(II) and Palladium and Platinum Porphyrinic Components: Impact of Heavy Metals upon Supermolecular Electro-Optic Properties

A new series of strongly coupled oscillators based upon (porphinato)Pd, (porphinato)Pt, and bis(terpyridyl)-ruthenium(II) building blocks is described. These RuPPd, RuPPt, RuPPdRu, and RuPPtRu chromophores feature bis- (terpyridyl)Ru(II) moieties connected to the (porphinato)metal unit via an ethyne linker that bridges the 4!-terpyridyl and porphyrin macrocycle meso-carbon positions. Pump–probe transient optical data demonstrate sub-picosecond excited singlet-to-triplet-state relaxation. The relaxed lowest-energy triplet (T 1 ) excited states of these chromophores feature absorption manifolds that span the 800–1200 nm spectral region, microsecond triplet-state lifetimes, and large absorptive extinction coefficients [ε(T 1 → T n ) > 4 × 10 4 M –1 cm –1 ]. Dynamic hyperpolarizability (β λ ) values were determined from hyper-Rayleigh light scattering (HRS) measurements carried out at several incident irradiation wavelengths over the 800–1500 nm spectral region. Relative to benchmark RuPZn and RuPZnRu chromophores which showed large βHRS values over the 1200–1600 nm range, RuPPd, RuPPt, RuPPdRu, and RuPPtRu displayed large βHRS values over the 850–1200 nm region. Generalized Thomas–Kuhn sum (TKS) rules and experimental hyperpolarizability values were utilized to determine excited state-to-excited state transition dipole terms from experimental electronic absorption data and thus assessed frequency-dependent β λ values, including two- and three-level contributions for both β zzz and β xzx tensor components to the RuPPd, RuPPt, RuPPdRu, and RuPPtRu hyperpolarizability spectra. Furthermore, these analyses qualitatively rationalize how the βzzz and βxzx tensor elements influence the observed irradiation wavelength-dependent hyperpolarizability magnitudes. The TKS analysis suggests that supermolecules related to RuPPd, RuPPt, RuPPdRu, and RuPPtRu will likely feature intricate dependences of experimentally determined βHRS values as a function of irradiation wavelength that derive from substantial singlet–triplet mixing, and complex interactions among multiple different β tensor components that modulate the long wavelength regime of the nonlinear optical response.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1992

Enhancing The Hyperpolarizabilities Of Finite Polyenes

Improved strategy for exploiting unusual optical properties to enhance molecular hyperpolarizabilities by introducing "defect" quantum-mechanical states and produce molecules switched photochemically or electrochemically between states characterized by different second molecular hyperpolarizabilities. Strategy, conjugation and/or substitution defects, electrically neutral or charged dopant orimpurity atoms or groups thereof, incorporated into finite polyene. Defects in finite polyenes alter second molecular hyperpolarizabilities. Transient large second hyperpolarizabilities attainable in molecules of structure II.

Beratan, David N.↗
DOE OSTI2023

DFT-Based Calculation of Molecular Hyperpolarizability and SFG Intensity of Symmetric and Asymmetric Stretch Modes of Alkyl Groups

Vibrational sum frequency generation (SFG) spectroscopy has been extensively used for obtaining structural information of molecular functional groups at two-dimensional (2D) interfaces buried in the gas or liquid medium. Although the SFG experiment can be done elegantly, interpreting the measured intensity in terms of molecular orientation with respect to the lab coordinate is quite complicated. One of the main reasons is the difficulty of determining the hyperpolarizability tensors of even simple molecules that govern their SFG responses. The single-bond polarizability derivative (SBPD) model has been proposed to estimate the relative magnitude of SFG-active hyperpolarizability by assuming that the perturbation associated to each vibration is negligible. In this study, density functional theory (DFT) was used to calculate the polarizability and dipole derivative tensors of the CH 3 stretch mode of CH 3 I, CH 3 CH 2 I, CH 3 OH, CH 3 CH 2 OH. Then, the hyperpolarizability tensors of symmetric and asymmetric vibration modes were calculated considering the Boltzmann distribution of representative conformers, which allowed theoretical calculation of their SFG intensities at all polarization combinations as a function of the tilt angle of the CH 3 group with respect to the surface normal direction. Then the ratios of the calculated SFG intensities for the CH 3 peaks used in experimental studies for the CH 3 tilt angle determination were compared. This comparison clearly showed the effect of vibrational coupling among neighboring functional groups. As a result, this study presents new parameters that can be used in determining the average tilt angle of the CH 3 group at the 2D interface with SFG measurements as well as limitations of the method.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1992

Connected triple excitations in coupled-cluster calculations of hyperpolarizabilities: Neon

We have calculated the second hyperpolarizability gamma of neon using the CCSD(T) method. The accuracy of the CCSD(T) approach has been established by explicit comparison with the single, double and triple excitation coupled-cluster (CCSDT) method using extended basis sets that are known to be adequate for the description of gamma. Our best estimate for gamma(sub 0) of 110 +/- 3 a.u. is in good agreement with other recent theoretical values and with Shelton's recent experimental estimate of 108 +/- 2 a.u. Comparison of the MP2 and CCSD(T) hyperpolarizability values indicates that MP2 gives a very good description of the electron correlation contribution to gamma(sub 0). We have combined MP2 frequency-dependent corrections with the CCSD(T) gamma(sub 0) to yield values of gamma(-2 omega;omega,omega,0) and gamma(exp K)(-omega;omega,0,0).

Rice, Julia E.↗
NASA NTRS1993

Relation between bond-length alternation and second electronic hyperpolarizability of conjugated organic molecules

The solvent dependence of the second hyperpolarizability, gamma, of a variety of unsaturated organic compounds has been measured by third harmonic generation at 1907 nanometers. It is seen that the measured gamma is a function of solvent polarity. These solvent-dependent hyperpolarizabilities are associated with changes in molecular geometry from a highly bond-length alternated, polyenelike structure for a formyl-substituted compound in nonpolar solvents, to a cyaninelike structure, with little bond-length alternation, for a dicyanovinyl-substituted compound in polar solvents. By tuning bond-length alternation, gamma can be optimized in either a positive or negative sense for polymethine dyes of a given conjugation length.

Marder, Seth R.↗
NASA NTRS1993

Optimization of the First and Second Hyperpolarizabilities of Organic Dyes (abstract)

We have been attempting to correlate hyperpolarizabilities with bond-length alteration (BLA), which is defined as the difference in the average length between adjacent carbon-carbon bonds in a polymethine [(CH)(sub n)] Polyenes have alternating double and single bonds (bond length equal to 1.34 Sand 1.45 U respectively), and thus show a high degree of bond-length alteration (BLA = -0.11 u.

organic dyes carbon-carbon bonds hyperpolarizabili↗
NASA NTRS1993

Experimental Demonstration of the Dependence of the First Hyperpolarizability of Donor-Acceptor Substituted Polyenes on the Ground-State Polarization and Bond Length Alternation

The dependence of the product of the first hyperpolarizability, beta, and the ground-state dipole moment, mu, for a series of donor-acceptor polyenes with a large range of ground-state polarization, was measured in a variety of solvents by electric field induced second harmonic generation. The observed behavior of mu times beta as a function of ground-state polarization agrees well with theoretical predictions. In particular, as a function of increasing polarization, mu times beta was found to first increase, peak in a positive sense, decrease, pass through zero, become large and negative, and eventually peak in a negative sense.

hyperpolarizability donor-acceptor substituted pol↗
NASA NTRS1989

Influence of gap states on the nonresonant second hyperpolarizabilities of conjugated organic polymers

The presence of conjugation and substitution defects introduces gap states in finite polyenes that are shown to influence the size and sign of the second molecular hyperpolarizability (SMH). Using a one-electron tight-binding model, the dependence of SMH on the defect-state occupancy and energy in finite polyenes is calculated. Defects can cause a significant decrease or enhancement of SMH by impeding charge delocalization or by creating partly filled bands (mimicking the one-band limit), respectively. Concomitant sign changes in SMH are predicted. Calculation results suggest strategies for designing molecules that can be either photochemically or electrochemically switched between states with considerably different SMHs.

Beratan, David N.↗
NASA NTRS1991

Approaches for optimizing the first electronic hyperpolarizability of conjugated organic molecules

Conjugated organic molecules with electron-donating and -accepting moieties can exhibit large electronic second-order nonlinearities, or first hyperpolarizabilities, beta. The present two-state, four-orbital independent-electron analysis of beta leads to the prediction that its absolute value will be maximized at a combination of donor and acceptor strengths for a given conjugated bridge. Molecular design strategies for beta optimization are proposed which give attention to the energetic manipulations of the bridge states. Experimental results have been obtained which support the validity of this approach.

Marder, S. R.↗
NASA NTRS1990

Theoretical study of polarizabilities and hyperpolarizabilities of Ne, HF, F(-), and OH(-)

Theoretical calculations are presented for the polarizability parameters through the fourth power of an applied static electric field for Ne and HF and through the second power in the field for the negative ions F(-) and OH(-). Large Gaussian basis sets are employed and electron correlation is incorporated using the modified coupled pair functional (MCPF) method and for Ne and HF using coupled-cluster single- and double-excitation (CCSD) methods with two approaches of including the effect of triple excitations. The MCPF method is found to perform well in relation to the more rigorous CCSD method.

Chong, Delano P.↗
NASA NTRS1989

The polarizabilities of neon

The static dipole polarizability, second hyperpolarizability, quadrupole polarizability and dipole-dipole-quadrupole hyperpolarizability for the Ne atom are computed, using large Gaussian basis sets and coupled cluster wavefunctions. Correlation effects are substantial, ranging from 15 percent for the dipole polarizability to 40 percent for the second hyperpolarizability. It is confirmed by explicit calculation earlier hypotheses that g-type and higher angular momentum functions and core correlation effects make almost no contribution to these properties in Ne. Triple excitations, on the other hand, are very important, accounting for as much as 25 percent of the correlation contribution to the second hyperpolarizability. The best estimate of the second hyperpolarizability is 119 + or - 4 au, in good agreement with the recent calculations of Maroulis and Thakkar (1989) and the latest experimental result of Shelton (1989).

Taylor, Peter R.↗
NASA NTRS1987

Nonlinear susceptibilities of finite conjugated organic polymers

Tight-binding calculations of the length dependence of the third-order molecular hyperpolarizability for polyenes and polyynes are reported. The pi-electron wave functions were determined by exploiting the limited translational symmetry of the molecules. Perturbation theory was used to calculate the longitudinal component of the electronic nonresonant hyperpolarizability. This is the first two-'band' calculation of third-order hyperpolarizabilities on finite pi-electron systems of varying length. In contrast to the results of the one-'band' models, the hyperpolarizability densities increase rapidly and then, after about 10-15 repeating units, approach an asymptotic value.

Beratan, David N.↗
NASA NTRS1993

Prediction of nonlinear optical properties of organic materials. General theoretical considerations

The prediction of nonlinear optical properties of organic materials is geared to assist materials scientists in the selection of good candidate molecules. A brief summary of the quantum mechanical methods used for estimating hyperpolarizabilities will be presented. The advantages and limitations of each technique will be discussed. Particular attention will be given to the finite-field method for calculating first and second order hyperpolarizabilities, since this method is better suited for large molecules. Corrections for dynamic fields and bulk effects will be discussed in detail, focusing on solvent effects, conformational isomerization, core effects, dispersion, and hydrogen bonding. Several results will be compared with data obtained from third-harmonic-generation (THG) and dc-induced second harmonic generation (EFISH) measurements. These comparisons will demonstrate the qualitative ability of the method to predict the relative strengths of hyperpolarizabilities of a class of compounds. The future application of molecular mechanics, as well as other techniques, in the study of bulk properties and solid state defects will be addressed. The relationship between large values for nonlinear optical properties and large conjugation lengths is well known, and is particularly important for third-order processes. For this reason, the materials with the largest observed nonresonant third-order properties are conjugated polymers. An example of this type of polymer is polydiacetylene. One of the problems in dealing with polydiacetylene is that substituents which may enhance its nonlinear properties may ultimately prevent it from polymerizing. A model which attempts to predict the likelihood of solid-state polymerization is considered, along with the implications of the assumptions that are used. Calculations of the third-order optical properties and their relationship to first-order properties and energy gaps will be discussed. The relationship between monomeric and polymeric third-order optical properties will also be considered.

Cardelino, B.↗
DOE OSTI2026

Multiresolution Quantum Chemistry: Nonlinear Response Properties at the Basis Set Limit

We benchmark the accuracy of Dunning correlation-consistent Gaussian basis sets for computing frequencydependent second-order hyperpolarizabilities relevant to second-harmonic generation (SHG), using multiresolution analysis (MRA) as a reference. Basis set errors are analyzed using a unit-sphere representation of the effective hyperpolarizability vector, enabling direct assessment of directional error structure. We introduce a relative RMS total error metric that integrates directional deviations over the unit sphere and complement it with signed projection errors that distinguish over- and underestimation. Unsupervised clustering based on these signed directional metrics reveals four distinct convergence behaviors across a set of 68 molecules. Unitsphere visualizations of representative systems show that basis set errors are often highly anisotropic and localized along specific bond directions, even when global error measures appear small. Doubly augmented basis sets consistently outperform singly augmented ones, and core-polarization functions are required for uniform convergence in second-row systems. Overall, this work demonstrates that directional analysis combined with clustering provides a robust framework for understanding basis set convergence in nonlinear optical response properties.

Basis sets↗