Ab initio study of the nonlinear optical properties of urea: Electron correlation and dispersion effects

We present the results of ab initio calculations on the first-, second-, and third-order molecular polarizabilities of urea. An efficacious general finite field perturbation approach, previously applied in the case of paranitroaniline, is extended to the evaluation of axial and nonaxial components of the nonlinear responses. The validity of our numerical procedure is examined at the Hartree–Fock level of theory by comparison with analytical derivative results. The impact of electron correlation is analyzed, by calculating the optical nonlinearities at the Moller-Plesset perturbation theory level. The second-order Moller-Plesset electron correlation correction is shown: (i) to enhance the third-order polarizability y by almost a factor of 2 and (ii) to include the major correlation effects as consideration of the fourth-order correction further improves the y components by less than 20%. We also discuss the frequency-dependence of the nonlinear optical properties of urea by presenting calculations of the dynamic components at the noncorrelated level of theory for different optical processes. © 1995 John Wiley & Sons, Inc.

[1]  Seth R. Marder,et al.  Electric Field Modulated Nonlinear Optical Properties of Donor-Acceptor Polyenes: Sum-Over-States Investigation of the Relationship between Molecular Polarizabilities (.alpha., .beta., and .gamma.) and Bond Length Alternation , 1994 .

[2]  P. Prasad,et al.  Nonlinear optical properties of novel thiophene derivatives: Experimental and abinitio time‐dependent coupled perturbed Hartree–Fock studies , 1993 .

[3]  D. Dudis,et al.  Vibronic contribution to static molecular hyperpolarizabilities , 1993 .

[4]  J. Perry,et al.  Relation Between Bond-Length Alternation and Second Electronic Hyperpolarizability of Conjugated Organic Molecules , 1993, Science.

[5]  D. M. Bishop,et al.  Calculation of vibrational dynamic hyperpolarizabilities for H2O, CO2, and NH3 , 1993 .

[6]  Michel Dupuis,et al.  Electron correlation effects in hyperpolarizabilities of p-nitroaniline , 1993 .

[7]  D. Dixon,et al.  Semiempirical calculations of hyperpolarizabilities for extended π systems : polyenes, polyynes, and polyphenyls , 1992 .

[8]  David A. Dixon,et al.  Semiempirical calculations of hyperpolarizabilities for donor-acceptor molecules: comparison to experiment , 1992 .

[9]  P. Jørgensen,et al.  Frequency-dependent hyperpolarizability of hydrogen fluoride , 1992 .

[10]  Prasad,et al.  Frequency dependence of linear and nonlinear optical properties of conjugated polyenes: An ab initio time-dependent coupled Hartree-Fock study. , 1992, Physical review. A, Atomic, molecular, and optical physics.

[11]  P. Prasad,et al.  Dispersion of linear and nonlinear optical properties of benzene: An ab initio time‐dependent coupled‐perturbed Hartree–Fock study , 1991 .

[12]  M. Dupuis,et al.  Hydrogen bonds and (hyper)polarizabilities in molecular crystals : an ab initio SCF study of urea , 1991 .

[13]  Seth R. Marder,et al.  Materials for Nonlinear Optics Chemical Perspectives , 1991 .

[14]  R. Bartlett,et al.  Hyperpolarizabilities of molecules with frequency dependence and electron correlation , 1991 .

[15]  S. Karna,et al.  Frequency dependent nonlinear optical properties of molecules: Formulation and implementation in the HONDO program , 1991 .

[16]  M. Spackman Time‐dependent Hartree–Fock second‐order molecular properties with a moderately sized basis set. I. The frequency dependence of the dipole polarizability , 1991 .

[17]  P. Prasad,et al.  Nonlinear optical properties of p‐nitroaniline: An ab initio time‐dependent coupled perturbed Hartree–Fock study , 1991 .

[18]  N. Handy,et al.  Frequency dependent hyperpolarizabilities with application to formaldehyde and methyl fluoride , 1990 .

[19]  P. Prasad,et al.  Theoretical and experimental studies of optical nonlinearities of haloforms CHX3, X=F, Cl, Br, I , 1990 .

[20]  M. Spackman Accurate prediction of static dipole polarizabilities with moderately sized basis sets , 1989 .

[21]  P. Prasad,et al.  Ab initio calculations of polarizability and second hyperpolarizability in benzene including electron correlation treated by Møller-Plesset theory , 1989 .

[22]  B. Pierce A theoretical analysis of third‐order nonlinear optical properties of linear polyenes and benzene , 1989 .

[23]  Michel Dupuis,et al.  Ab initio analytic polarizability, first and second hyperpolarizabilities of large conjugated organic molecules: Applications to polyenes C4H6 to C22H24 , 1988 .

[24]  C. W. Dirk,et al.  The contribution of π electrons to second harmonic generation in organic molecules , 1986 .

[25]  Hideo Sekino,et al.  Frequency dependent nonlinear optical properties of molecules , 1986 .

[26]  R. Bartlett,et al.  Hyperpolarizabilities of the hydrogen fluoride molecule: A discrepancy between theory and experiment? , 1986 .

[27]  Joseph Zyss,et al.  Influence of the molecular environment in solution measurements of the Second-order optical susceptibility for urea and derivatives , 1982 .

[28]  J. Zyss,et al.  Nonlinear optical properties of organic crystals with hydrogen‐bonded molecular units: The case of urea , 1982 .

[29]  R. Bartlett,et al.  Molecular hyperpolarizabilities. I. Theoretical calculations including correlation , 1979 .

[30]  Ian M. Mills,et al.  Force Constants and Dipole-Moment Derivatives of Molecules from Perturbed Hartree-Fock Calculations. I , 1968 .

[31]  H. A. Levy,et al.  The positions of hydrogen atoms in urea by neutron diffraction , 1957 .

[32]  André Persoons,et al.  THIRD-ORDER NONLINEAR OPTICAL RESPONSE IN ORGANIC MATERIALS : THEORETICAL AND EXPERIMENTAL ASPECTS , 1994 .

[33]  David J. Williams,et al.  Introduction to Nonlinear Optical Effects in Molecules and Polymers , 1991 .

[34]  James J. P. Stewart,et al.  Calculation of the nonlinear optical properties of molecules , 1990 .

[35]  J. Ladik,et al.  Quantum theory of polymers as solids , 1988 .

[36]  W. Lipscomb,et al.  Perturbed Hartree—Fock Calculations. I. Magnetic Susceptibility and Shielding in the LiH Molecule , 1963 .