Modeling Nonlinear Optical Properties of Transition Metal Complexes. Basis Set, Effective Core Potential, and Geometry Effects

Description:

Article discussing modeling nonlinear optical properties of transition metal complexes and the basis set, effective core potential, and geometry effects.

Creator(s):
Creation Date: April 4, 1998
Partner(s):
UNT College of Arts and Sciences
Collection(s):
UNT Scholarly Works
Usage:
Total Uses: 156
Past 30 days: 5
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Creator (Author):
Cundari, Thomas R., 1964-

University of North Texas; University of Memphis

Creator (Author):
Kurtz, Henry A.

University of Memphis

Creator (Author):
Zhou, Tie

University of Memphis

Publisher Info:
Publisher Name: American Chemical Society
Place of Publication: [Washington, DC]
Date(s):
  • Creation: April 4, 1998
Description:

Article discussing modeling nonlinear optical properties of transition metal complexes and the basis set, effective core potential, and geometry effects.

Degree:
Department: Chemistry
Note:

Reprinted with permission from the Journal of Physical Chemistry A. Copyright 1998 American Chemical Society.

Note:

Abstract: Nonlinear optical (NLO) properties of transition metal complexes are studied using quantum chemical calculations. By comparison with all electron calculations, effective core potentials have been shown to be competent for the calculation of NLO properties as long as the valence basis sets are comparable. While overall the basis set effects are important for calculation of NLO properties, they are found to be less important for the central transition metal than for the surrounding ligands. Augmenting the basis set of main group elements with diffuse, s, p, and d functions in a proper way could provide the best compromise between speed and accuracy of the computation. Interesting trends are found in the calculation of NLO properties of [MO₄]q⁻. Both polarizability (α) and second hyperpolarizability (y) decrease toward the right across the transition series. The second series [MO₄]q⁻ have the largest α among the three metalates in a triad. For group IVB and VB complexes with larger charges (-4 and -3, respectively), the second series [MO₄]q⁻ have the largest y, while for groups VIB, VIIB, and VIII, with less anionic metalates (-2, -1, and 0, respectively), the third series metalates have the largest y. The relative difference in both α and y values among the three series in the same group is much smaller than between different groups. Overall, variations in the calculated values of NLO properties correlate with M-O bond lengths and hence the size of the metalate ion.

Physical Description:

5 p.

Language(s):
Subject(s):
Keyword(s): transition metal complexes | nonlinear optical | electrons | ligands
Source: Journal of Physical Chemistry A, 1998, Washington DC: American Chemical Society, pp. 2962-2966
Partner:
UNT College of Arts and Sciences
Collection:
UNT Scholarly Works
Identifier:
  • DOI: 10.1021/jp980438+ |
  • ARK: ark:/67531/metadc107805
Resource Type: Article
Format: Text
Rights:
Access: Public
Citation:
Publication Title: Journal of Physical Chemistry A
Volume: 102
Issue: 17
Page Start: 2962
Page End: 2966
Peer Reviewed: Yes