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Title: VIBRATIONAL SPECTRA AND NORMAL COORDINATE ANALYSIS OF NEPTUNIUM (IV) BOROHYDRIDE AND NEPTUNIUM (IV) BORODEUTERIDE

Abstract

Solid state, low temperature IR (25-7400 cm{sup -1}) and Raman (100-2600 cm{sup -1}) spectra were obtained for Np(BH{sub 4}){sub 4} and Np(BD{sub 4}){sub 4} from which most of the allowed fundamentals were assigned based on the T{sub d} molecular structure. Those assignments were used in a normal coordinate analysis to derive a simple force field using 8 primary and 5 interaction constants. This field is very similar to those found for Zr(BH{sb 4}){sub 4} and Hf(BH{sub 4}){sub 4}. Isotopic impurity, overtone, and combination bands were identified in the IR spectra with the help of the normal coordinate calculations. Near IR spectra of Zr(BH{sub 4}){sub 4} and Zr(BD{sub 4}({sub 4} were taken in the range 7400-4000 cm{sup -1} and the observed absorption bands were assigned as either overtone or combination levels.

Authors:
;
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
Materials Sciences Division
OSTI Identifier:
1070010
Report Number(s):
LBL-10901
Journal ID: ISSN 0021-9606
DOE Contract Number:
DE-AC02-05CH11231
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 73; Journal Issue: 8
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Banks, Rodney H., and Edelstein, Norman. VIBRATIONAL SPECTRA AND NORMAL COORDINATE ANALYSIS OF NEPTUNIUM (IV) BOROHYDRIDE AND NEPTUNIUM (IV) BORODEUTERIDE. United States: N. p., 1980. Web. doi:10.1063/1.440584.
Banks, Rodney H., & Edelstein, Norman. VIBRATIONAL SPECTRA AND NORMAL COORDINATE ANALYSIS OF NEPTUNIUM (IV) BOROHYDRIDE AND NEPTUNIUM (IV) BORODEUTERIDE. United States. doi:10.1063/1.440584.
Banks, Rodney H., and Edelstein, Norman. Sun . "VIBRATIONAL SPECTRA AND NORMAL COORDINATE ANALYSIS OF NEPTUNIUM (IV) BOROHYDRIDE AND NEPTUNIUM (IV) BORODEUTERIDE". United States. doi:10.1063/1.440584. https://www.osti.gov/servlets/purl/1070010.
@article{osti_1070010,
title = {VIBRATIONAL SPECTRA AND NORMAL COORDINATE ANALYSIS OF NEPTUNIUM (IV) BOROHYDRIDE AND NEPTUNIUM (IV) BORODEUTERIDE},
author = {Banks, Rodney H. and Edelstein, Norman},
abstractNote = {Solid state, low temperature IR (25-7400 cm{sup -1}) and Raman (100-2600 cm{sup -1}) spectra were obtained for Np(BH{sub 4}){sub 4} and Np(BD{sub 4}){sub 4} from which most of the allowed fundamentals were assigned based on the T{sub d} molecular structure. Those assignments were used in a normal coordinate analysis to derive a simple force field using 8 primary and 5 interaction constants. This field is very similar to those found for Zr(BH{sb 4}){sub 4} and Hf(BH{sub 4}){sub 4}. Isotopic impurity, overtone, and combination bands were identified in the IR spectra with the help of the normal coordinate calculations. Near IR spectra of Zr(BH{sub 4}){sub 4} and Zr(BD{sub 4}({sub 4} were taken in the range 7400-4000 cm{sup -1} and the observed absorption bands were assigned as either overtone or combination levels.},
doi = {10.1063/1.440584},
journal = {Journal of Chemical Physics},
number = 8,
volume = 73,
place = {United States},
year = {Sun Jun 01 00:00:00 EDT 1980},
month = {Sun Jun 01 00:00:00 EDT 1980}
}
  • Solid state, low temperature IR (25--7400 cm/sup -1/) and Raman (100--2600 cm/sup -1/) spectra were obtained for Np(BH/sub 4/)/sub 4/ and Np(BD/sub 4/)/sub 4/ from which most of the allowed fundamentals were assigned based on the T/sub d/ molecular structure. Those assignments were used in a normal coordinate analysis to derive a simple force field using eight primary and five interaction constants. This field is very similar to those found for Zr(BH/sub 4/)/sub 4/ and Hf(BH/sub 4/)/sub 4/. Isotopic impurity, overtone, and combination bands were identified in the IR spectra with the help of the normal coordinate calculations. Near IRmore » spectra of Zr(BH/sub 4/)/sub 4/ and Zr(BD/sub 4/)/sub 4/ were taken in the range 7400--4000 cm/sup -1/ and the observed absorption bands were assigned as either overtone or combination levels.« less
  • A systematic investigation was carried out of the vibrational spectra of the hydrogen peroxide crystal and its deuterated analogue, using both ir and Raman spectroscopy, over the range 4000 to 50 cm/sup -1/. Mixtures of the two isotopic species up to approximately 95% deuteration were also studied to identify the fundamentals of the hybrid molecule, HDO/sub 2/. Single crystals of hydrogen peroxide oriented along two of the three crystallographic axes were examined in the Raman effect with polarized laser light. The O-H stretching bands are remarkably narrow in the Raman spectra: DELTA nu (1/2) = 20 cm/sup -1/ at --more » 193 deg C compared with about 50 cm/sup in the ir. Nearly all the O-H stretching components predicted by the factor group analysis were observed but a satisfactory identification of all components of the OOH deformation modes could not be achieved. The O-O stretching frequency in D/sub 2/O/sub 2/ (872 cm/sup -1/ ) is slightly higher than in H/sub 2/O/sub 2/ (871 cm/sup -1/) co ntrary to expectations. The hydrogen bonds in the H/sub 2/O/sub 2/ crystal appear somewhat less strong (by about 10 to 15%) than those in ice. A normal coordinate analysis of the unit cell modes proved to be of considerable value in the assignment of observed frequencies. The values of the eleven principal force constants and the twenty interaction constants used to fit the 59 assigned frequencies appear reasonable and are comparable with values found for other hydrogen bonded systems. (auth)« less
  • The infrared and resonance Raman spectra of the tris(bipyridine)ruthenium(II) complex and several of its deuteriated analogues are reported: specifically, those of the complexes of 3,3'-dideuterio-2,2'-bipyridine, 6,6'-dideuterio-2,2'-bipyridine, and perdeuterio-2,2'-bipyridine. Multiple excitation lines are employed to obtain the resonance Raman spectra to facilitate observation of all A/sub 1/ fundamental vibrations associated with the ligand framework. Normal-coordinate calculations are carried out employing a systematic procedure based on a modified valence force field that is comparable to those used previously for aromatic molecules. The resultant (30-force constant) field reproduced observed frequencies with an average error or approx. 1.5%.
  • The Raman spectra of Cl{sub 3}PN(PCl{sub 2}N){pi}P(O)Cl{sub 2} and [Cl{sub 3}PN(PCl{sub 2}N){pi}PCl{sub 3}]{sup +}PCl{sub 6}{sup {minus}} (n = 1,2) were recorded in the solid and liquid states at different temperatures. The qualitative depolarization ratios were obtained in the liquid phase. A {sup 31}P NMR study for the molecular compounds showed a coalescence phenomenon near 220 K. The potential energy around the PN bonds for the Cl{sub 3}PN(PCl{sub 2}N)P(O)Cl{sub 2} molecule and [Cl{sub 3}PN(PCl{sub 2}N){sub 2}PCl{sub 3}]{sup +} cation are derived from MNDO (modified neglect of diatomic overlap) calculations. The stable conformations are found to be trans-cis for Cl{sub 3}PN(PCl{sub 2}N)P(O)Cl{submore » 2} and [Cl{sub 3}PN(PCl{sub 2}N){sub 2}PCl{sub 3}]{sup +}. The calculated structural parameters agree well with the X-ray experimental data. The frequencies obtained by normal coordinate analysis are in good agreement with the observed ones. The MNDO calculation of the harmonic force field is in reasonable agreement with the experimental values. The force constant values assigned to torsional modes around the PN bonds correspond to low barriers for the internal rotations. The easy internal rotation around the P-N and P{double_bond}N bonds can explain the flexibility of the phosphazene backbone and the elastomeric properties of the phosphazene polymers. 46 refs., 6 figs., 3 tabs.« less