Nitrogen and oxygen donors in nonlinear optical materials: Effects of alkyl vs phenyl substitution on the molecular hyperpolarizability

Journal of the American Chemical Society

Volumn 118, Issue 41, 1996, Pages 9966-9973

  Whitaker, Craig M ^a   Patterson, Eric V ^a   Kott, Kevin L ^a   McMahon, Robert J ^a  

^a Wisconsin Electric Machines and Power Electronics Consortium   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AMINE; ETHER DERIVATIVE;

ARTICLE; DIPOLE; MOLECULAR DYNAMICS; THEORY;

EID: 0029917439     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja960284g     Document Type: Article

References (70)

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42. ZINDO version 95.0; Molecular Simulations, Inc.: San Diego, CA 1995. In the course of the current investigation, we realized that the ZINDO code, as provided by BIOSYM, failed to reproduce electronic absorption spectra, dipole moments, polarizabilities, and hyperpolarizabilities previously attributed to the same algorithm (see; Kanis, D. R.; Marks, T. J.; Ratner, M. A. Int. J. Quantum Chem. 1992, 43, 61-82). BIOSYM traced the discrepancy to the parametrization for oxygen. The default oxygen parameter is best suited to modeling solvent effects, while a different oxygen parameter is required to model polarizabilities and hyperpolarizabilities. After changing the oxygen parameter, the ZINDO code indeed reproduces all of the data published by Kanis et al. Users of BIOSYM's ZINDO code should note that this subtlety was not recognized until August 1995. Thus, all versions of ZINDO supplied by BIOSYM before that date were not correctly parametrized for computing hyperpolarizabilities of oxygen-containing compounds. The ZINDO values contained in Whitaker, C. M. Ph.D. Dissertation, University of Wisconsin-Madison, 1995, are all incorrect, and have been recomputed for the purposes of this publication.
43. ZINDO version 95.0; Molecular Simulations, Inc.: San Diego, CA 1995. In the course of the current investigation, we realized that the ZINDO code, as provided by BIOSYM, failed to reproduce electronic absorption spectra, dipole moments, polarizabilities, and hyperpolarizabilities previously attributed to the same algorithm (see; Kanis, D. R.; Marks, T. J.; Ratner, M. A. Int. J. Quantum Chem. 1992, 43, 61-82). BIOSYM traced the discrepancy to the parametrization for oxygen. The default oxygen parameter is best suited to modeling solvent effects, while a different oxygen parameter is required to model polarizabilities and hyperpolarizabilities. After changing the oxygen parameter, the ZINDO code indeed reproduces all of the data published by Kanis et al. Users of BIOSYM's ZINDO code should note that this subtlety was not recognized until August 1995. Thus, all versions of ZINDO supplied by BIOSYM before that date were not correctly parametrized for computing hyperpolarizabilities of oxygen-containing compounds. The ZINDO values contained in Whitaker, C. M. Ph.D. Dissertation, University of Wisconsin-Madison, 1995, are all incorrect, and have been recomputed for the purposes of this publication.
44. ZINDO version 95.0; Molecular Simulations, Inc.: San Diego, CA 1995. In the course of the current investigation, we realized that the ZINDO code, as provided by BIOSYM, failed to reproduce electronic absorption spectra, dipole moments, polarizabilities, and hyperpolarizabilities previously attributed to the same algorithm (see; Kanis, D. R.; Marks, T. J.; Ratner, M. A. Int. J. Quantum Chem. 1992, 43, 61-82). BIOSYM traced the discrepancy to the parametrization for oxygen. The default oxygen parameter is best suited to modeling solvent effects, while a different oxygen parameter is required to model polarizabilities and hyperpolarizabilities. After changing the oxygen parameter, the ZINDO code indeed reproduces all of the data published by Kanis et al. Users of BIOSYM's ZINDO code should note that this subtlety was not recognized until August 1995. Thus, all versions of ZINDO supplied by BIOSYM before that date were not correctly parametrized for computing hyperpolarizabilities of oxygen-containing compounds. The ZINDO values contained in Whitaker, C. M. Ph.D. Dissertation, University of Wisconsin-Madison, 1995, are all incorrect, and have been recomputed for the purposes of this publication.
45. We used AM1-optimized geometries for the ZINDO computations.
46. All VAMP hyperpolarizabilities were computed with configuration interaction involving 12 active orbitals (PECI = 12; corresponds to a sum over 73 singlet excited states). Calculations involving 8 and 10 active orbitals (corresponding to 33 and 51 singlet excited states, respectively) established that the sum-over-states calculations reached convergence.
47. All ZINDO hyperpolarizabilities were computed with configuration interaction involving 145 determinants corresponding to the 145 lowest singlet states.
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58. 35-37 The nonbonding electron pair on nitrogen is not the HOMO; in aniline itself, the nonbonding electron pair is HOMO -2. (This fact is not widely appreciated in the nonlinear optics community.) An alkyl substituent raises the energy of both the nonbonding electron pair and the HOMO.
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60. Molecular orbital diagrams (AMI) and tables of excited states which may contribute to hyperpolarizability for compounds 1-9 are available as supporting information.
61. ZINDO calculations indicate that the first excited states of 1, 2, and 3 can be described predominantly (ca. 95%) in terms of HOMO-LUMO excitation. This is not the case for the first excited states of 4 and 5. Although HOMO-LUMO excitation remains the largest single contributor (ca. 80%), other electronic configurations cannot be neglected (20%).
62. aryl-N, 1.388 Å; C-O-C angle, 116°; C-N-C angle, 124°. Computed values based on AM1-optimized geometry.
63. 32).
64. 3. The small blue-shift of 9 vs 4 suggests a slightly greater deviation from planarity for biphenyl 9 than for diphenylamine 4.
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