Ultraviolet Resonant Raman Enhancements in the Detection of ...

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excitation. Total accumulated CCD integration time for all spectra was 180 seconds. ....................................................................................................72  Figure 36.  Raman spectra of 2.43 mM 2,4-DNT in acetonitrile recorded at various laser power settings ranging from 25 µW to 0.95 mW using 229 nm laser excitation. Total accumulated CCD integration time for all spectra was 180 seconds. ....................................................................................................73  xii
LIST OF TABLES Table 1. Table of select vibrational frequencies important in the analysis of high explosives (After: [17]). ..................................................................................18 Table 2. Calculated and reference maximum molar absorptivities for the primary transitions observed at wavelengths >220 nm for PNT; 2,4-DNT; and 2,4,6-TNT in acetonitrile. Reference values for PNT and 2,4-DNT were obtained using n-heptane as a solvent and 2,4,6-TNT was observed in cyclohexane [42]. ........................................................................................44 Table 3. Total Raman enhancements compared to NIR Raman measurements, which factors in frequency enhancements and local field effects, are presented for TNT and PETN solids divided by the depth of the sample in microns. For TNT, the total enhancements for solids are of the same order of the resonance enhancements for solutions for micron size samples. For PETN, which has less laser absorption and Raman signal self-absorption, total enhancements are estimated to be greater than enhancements in solution. ...........................................................................................................61 xiii
Page 1 and 2: LLNL-TH-413751 Ultraviolet Resonant
Page 3 and 4: NAVAL POSTGRADUATE SCHOOL MONTEREY,
Page 5 and 6: REPORT DOCUMENTATION PAGE Form Appr
Page 7 and 8: Approved for public release; distri
Page 9 and 10: ABSTRACT Raman-based spectroscopy i
Page 11 and 12: TABLE OF CONTENTS I.  INTRODUCTIO
Page 13 and 14: LIST OF FIGURES Figure 1.  Weight
Page 15: Figure 25.  Calculated Raman reso
Page 19 and 20: ACKNOWLEDGMENTS Foremost I wish to
Page 21 and 22: A. MOTIVATION I. INTRODUCTION The
Page 23 and 24: C. RESEARCH GOALS The primary goal
Page 25 and 26: II. DETECTION OF EXPLOSIVES A. SELE
Page 27 and 28: B. SPECTROSCOPY OF EXPLOSIVES Spect
Page 29 and 30: The presence of explosive related m
Page 31 and 32: While direct standoff detection of
Page 33 and 34: the explosive may be located in dif
Page 35 and 36: III. FUNDAMENTALS OF RAMAN SPECTROS
Page 37 and 38: thermal energy, a very small quanti
Page 39 and 40: Figure 5. Raman spectra of chlorofo
Page 41 and 42: Electronic State Virtual States n V
Page 43 and 44: Shot noise is a fundamental phenome
Page 45 and 46: IV. PREVIOUS RAMAN RESEARCH A. RAMA
Page 47 and 48: Sharma and collaborators at the Uni
Page 49 and 50: A. RAMAN CROSS SECTIONS V. METHOD T
Page 51 and 52: and ratioed to the same equation ev
Page 53 and 54: signal can be self-absorbed before
Page 55 and 56: enhancement multiplied by the frequ
Page 57 and 58: A. OBJECTIVES VI. EXPERIMENTAL TECH
Page 59 and 60: 1. NIR (785 nm) Raman System This R
Page 61 and 62: The manufacturer's wavelength calib
Page 63 and 64: A. SUMMARY OF RESULTS VII. RESULTS
Page 65 and 66: Figure 11. Calculated molar absorpt
Page 67 and 68:
strong. Since most molecules absorb
Page 69 and 70:
Figure 15. Raman spectra of PNT; 2,
Page 71 and 72:
Figure 17. Raman spectra of RDX usi
Page 73 and 74:
40x10 3 Intensity (A.U.) 30 20 10 0
Page 75 and 76:
scattering process, the Raman scatt
Page 77 and 78:
Figure 24. Calculated Raman resonan
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as the internal standard. For solid
Page 81 and 82:
The estimated total Raman enhanceme
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VIII. CONCLUSION A method was demon
Page 85 and 86:
IX. RECOMMENDATIONS In order to con
Page 87 and 88:
A. 785 NM SPECTRA 1. Standards APPE
Page 89 and 90:
Figure 31. Raman spectra of 3,4-DNT
Page 91 and 92:
Figure 33. Raman spectra of 3,4-DNT
Page 93 and 94:
30x10 3 Intensity (A.U.) 20 10 0 30
Page 95 and 96:
APPENDIX B. MATLAB CODE This source
Page 97 and 98:
B. PEAK AREA CALCULATIONS BASED ON
Page 99 and 100:
LIST OF REFERENCES [1] National Res
Page 101 and 102:
Spectra of 1,3,5-trinitro-1,3,5-tri
Page 103 and 104:
INITIAL DISTRIBUTION LIST 1. Defens
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