Raman spectroscopic study of the uranyl sulphate mineral jáchymovite (UO2)8(SO4)(OH)14•13H2O

Raman spectra of jáchymovite, (UO2)8(SO4)(OH)14•13H2O, were studied, complemented with infrared spectra, and compared with published Raman and infrared spectra of uranopilite, [(UO2)6(SO4)O2(OH)6(H2O)6] •6H2O. Bands related to the stretching and bending vibrations of (UO2)2+, (SO4)2-, (OH)- and water molecules were assigned. U-O bond lengths in uranyl and O-H…O hydrogen bond lengths were calculated from the Raman and infrared spectra.

Theoretical and numerical investigation of plasmon nanofocusing in metallic tapered rods and grooves

Effective focusing of electromagnetic (EM) energy to nanoscale regions is one of the major challenges in nano-photonics and plasmonics. The strong localization of the optical energy into regions much smaller than allowed by the diffraction limit, also called nanofocusing, offers promising applications in nano-sensor technology, nanofabrication, near-field optics or spectroscopy. One of the most promising solutions to the problem of efficient nanofocusing is related to surface plasmon propagation in metallic structures. Metallic tapered rods, commonly used as probes in near field microscopy and spectroscopy, are of a particular interest. They can provide very strong EM field enhancement at the tip due to surface plasmons (SP’s) propagating towards the tip of the tapered metal rod. A large number of studies have been devoted to the manufacturing process of tapered rods or tapered fibers coated by a metal film. On the other hand, structures such as metallic V-grooves or metal wedges can also provide strong electric field enhancements but manufacturing of these structures is still a challenge. It has been shown, however, that the attainable electric field enhancement at the apex in the V-groove is higher than at the tip of a metal tapered rod when the dissipation level in the metal is strong. Metallic V-grooves also have very promising characteristics as plasmonic waveguides. This thesis will present a thorough theoretical and numerical investigation of nanofocusing during plasmon propagation along a metal tapered rod and into a metallic V-groove. Optimal structural parameters including optimal taper angle, taper length and shape of the taper are determined in order to achieve maximum field enhancement factors at the tip of the nanofocusing structure. An analytical investigation of plasmon nanofocusing by metal tapered rods is carried out by means of the geometric optics approximation (GOA), which is also called adiabatic nanofocusing. However, GOA is applicable only for analysing tapered structures with small taper angles and without considering a terminating tip structure in order to neglect reflections. Rigorous numerical methods are employed for analysing non-adiabatic nanofocusing, by tapered rod and V-grooves with larger taper angles and with a rounded tip. These structures cannot be studied by analytical methods due to the presence of reflected waves from the taper section, the tip and also from (artificial) computational boundaries. A new method is introduced to combine the advantages of GOA and rigorous numerical methods in order to reduce significantly the use of computational resources and yet achieve accurate results for the analysis of large tapered structures, within reasonable calculation time. Detailed comparison between GOA and rigorous numerical methods will be carried out in order to find the critical taper angle of the tapered structures at which GOA is still applicable. It will be demonstrated that optimal taper angles, at which maximum field enhancements occur, coincide with the critical angles, at which GOA is still applicable. It will be shown that the applicability of GOA can be substantially expanded to include structures which could be analysed previously by numerical methods only. The influence of the rounded tip, the taper angle and the role of dissipation onto the plasmon field distribution along the tapered rod and near the tip will be analysed analytically and numerically in detail. It will be demonstrated that electric field enhancement factors of up to ~ 2500 within nanoscale regions are predicted. These are sufficient, for instance, to detect single molecules using surface enhanced Raman spectroscopy (SERS) with the tip of a tapered rod, an approach also known as tip enhanced Raman spectroscopy or TERS. The results obtained in this project will be important for applications for which strong local field enhancement factors are crucial for the performance of devices such as near field microscopes or spectroscopy. The optimal design of nanofocusing structures, at which the delivery of electromagnetic energy to the nanometer region is most efficient, will lead to new applications in near field sensors, near field measuring technology, or generation of nanometer sized energy sources. This includes: applications in tip enhanced Raman spectroscopy (TERS); manipulation of nanoparticles and molecules; efficient coupling of optical energy into and out of plasmonic circuits; second harmonic generation in non-linear optics; or delivery of energy to quantum dots, for instance, for quantum computations.

Raman spectroscopic study of the antimonate mineral brandholzite Mg[Sb(OH)12].6H2O

Raman spectra of brandholzite Mg[Sb(OH)6].6H2O were studied, complemented with infrared spectra, and related to the structure of the mineral. An intense Raman sharp band at 618 cm-1 is attributed to the SbO symmetric stretching mode. The low intensity band at 730 cm-1 is ascribed to the SbO antisymmetric stretching vibration. Low intensity Raman bands were found at 503, 526 and 578 cm-1. Corresponding infrared bands were observed at 527, 600, 637, 693, 741 and 788 cm-1. Four Raman bands observed at 1043, 1092, 1160 and 1189 cm-1 and eight infrared bands at 963, 1027, 1055, 1075, 1108, 1128, 1156 and 1196 cm-1 are assigned to δ SbOH deformation modes. A complex pattern resulting from the overlapping band of the water and hydroxyl units is observed. Raman bands are observed at 3240, 3383, 3466, 3483 and 3552 cm-1, infrared bands at 3248, 3434 and 3565 cm-1. The first two Raman bands and the first infrared band are assigned to water stretching vibrations. The two higher wavenumber Raman bands observed at 3466 and 3552 cm-1 and two infrared bands at 3434 and 3565 cm-1 are assigned to the stretching vibrations of the hydroxyl units. Observed Raman and infrared bands are connected with O-H…O hydrogen bonds and their lengths 2.72, 2.79, 2.86, 2.88 and 3.0 Å (Raman) and 2.73, 2.83 and 3.07 Å (infrared).

Raman spectroscopic study of the uranyl mineral pseudojohannite Cu6.5[(UO2)4O4(SO4)2]2(OH)5.25H2O

Raman spectra of pseudojohannite were studied and related to the structure of the mineral. Observed bands were assigned to the stretching and bending vibrations of (UO2)2+ and (SO4)2- units and of water molecules. The published formula of pseudojohannite is Cu6.5(UO2)8\[O8](OH)5\[(SO4)4].25H2O; however Raman spectroscopy does not detect any hydroxyl units. Raman bands at 805 and 810 cm-1 are assigned to (UO2)2+ stretching modes. The Raman bands at 1017 and 1100 cm-1 are assigned to the (SO4)2- symmetric and antisymmetric stretching vibrations. The three Raman bands at 423, 465 and 496 cm-1 are assigned to the (SO4)2- ν2 bending modes. The bands at 210 and 279 cm-1 are assigned to the doubly degenerate ν2 bending vibration of the (UO2)2+ units. U-O bond lengths in uranyl and O-H…O hydrogen bond lengths were calculated from the Raman and infrared spectra.

Raman spectroscopic study of the uranyl mineral metauranospinite Ca[(UO2)(AsO4)]2.8H2O

Raman spectra of metauranospinite Ca[(UO2)(AsO4)]2.8H2O complemented with infrared spectra were studied. Observed bands were assigned to the stretching and bending vibrations of (UO2)2+ and (AsO4)3- units and of water molecules. U-O bond lengths in uranyl and O-H…O hydrogen bond lengths were calculated from the Raman and infrared spectra.

Prehistoric hand stencils at Fern Cave, North Queensland (Australia): environmental and chronological implications of Raman spectroscopy and FT-IR imaging results

Raman spectroscopy and FT-IR imaging analyses of cave wall pigment samples from north Queensland (Australia) indicate that some hand stencils were undertaken during a dry environmental phase indicating late Holocene age. Other, earlier painting episodes also took place during dry environmental periods of the terminal Pleistocene and/or early Holocene. These results represent a rare opportunity to attain chronological information for rock art in conditions where insufficient carbon is present for radiocarbon dating.

Raman spectroscopic study of the antimonate mineral bahianite Al5Sb35+O14(OH)2

Raman spectroscopy has been used to characterise the antimonate mineral bahianite Al5Sb35+O14(OH)2 , a semi-precious gem stone. The mineral is characterised by an intense Raman band at 818 cm-1 assigned to Sb3O1413- stretching vibrations. Other lower intensity bands at 843 and 856 cm-1 are also assigned to this vibration and this concept suggests the non-equivalence of SbO units in the structure. Low intensity Raman bands at 669 and 682 cm-1 are probably assignable to the OSbO antisymmetric stretching vibrations. Raman bands at 1756, 1808 and 1929 cm-1 may be assigned to δ SbOH deformation modes, whilst Raman bands at 3462 and 3495 cm-1 are assigned to AlOH stretching vibrations. Complexity in the low wave number region is attributed to the composition of the mineral.

Raman spectroscopic study of the phosphate mineral Churchite-(Y) YPO4.2H2O

Raman spectroscopy has been used to study the rare earth mineral churchite-(Y) of formula (Y,REE)(PO4) •2H2O. The mineral contains yttrium and depending on the locality, a range of rare earth metals. The Raman spectra of two churchite-(Y) mineral samples from Jáchymov and Medvědín in the Czech Republic were compared with the Raman spectra of churchite-(Y) downloaded from the RRUFF data base. The Raman spectra of churchite-(Y) are characterized by an intense sharp band at 975 cm-1 assigned to the ν1 (PO4)3- symmetric stretching mode. A lower intensity band observed at around 1065 cm-1 is attributed to the ν3 (PO43-) antisymmetric stretching mode. The (PO43-) bending modes are observed at 497 cm-1 (ν2) and 563 cm-1(ν4). Some small differences in the band positions between the four churchite-(Y) samples from four different localities were found. These differences are possible to explain as different compositions of the churchite-(Y) minerals.

Raman spectroscopic study of the antimonate mineral lewisite (Ca,Fe,Na)2(Sb,Ti)2O6(O,OH)7

The mineral lewisite, (Ca,Fe,Na)2(Sb,Ti)2O6(O,OH)7 an antimony bearing mineral has been studied by Raman spectroscopy. A comparison is made with the Raman spectra of other minerals including bindheimite, stibiconite and roméite. The mineral lewisite is characterised by an intense sharp band at 517 cm-1 with a shoulder at 507 cm-1 assigned to SbO stretching modes. Raman bands of medium intensity for lewisite are observed at 300, 356 and 400 cm-1. These bands are attributed to OSbO bending vibrations. Raman bands in the OH stretching region are observed at 3200, 3328, 3471 cm-1 with a distinct shoulder at 3542 cm-1. The latter is assigned to the stretching vibration of OH units. The first three bands are attributed to water stretching vibrations. The observation of bands in the 3200 to 3500 cm-1 region suggests that water is involved in the lewisite structure. If this is the case then the formula may be better written as Ca, Fe2+, Na)2(Sb, Ti)2(O,OH)7 •xH2O.

Raman spectroscopic study of the antimonate mineral brizziite NaSbO3

Raman spectra of antimonate mineral brizziite NaSbO3 were studied and related to the structure of the mineral. Two sharp bands at 617 and 660 cm-1 are attributed to the SbO3- symmetric stretching mode. The reason for two symmetric stretching vibrations depends upon the bonding of the SbO3- units. The band at 617 cm-1 is assigned to bonding through the Sb and the 660 cm-1 to bonding through the oxygen. The low intensity band at 508 cm-1 is ascribed to the SbO antisymmetric stretching vibration. Low intensity bands were found at 503, 526 and 578 cm-1. Sharp Raman bands observed at 204, 230, 307 and 315 cm-1are assigned to OSbO bending modes. Raman spectroscopy enables a better understanding of the molecular structure of the mineral brizziite.

Raman spectroscopic study of the mineral finnemanite Pb5(As3+O3)3Cl

The arsenite minerals finnemanite Pb5(As3+O3)3Cl been studied by Raman spectroscopy. The most intense Raman band at 871 cm-1 is assigned to the ν1 (AsO3)3- symmetric stretching vibration. Three Raman bands at 898, 908 and 947 cm-1 are assigned to the ν3 (AsO3)3- antisymmetric stretching vibration. The observation of multiple antisymmetric stretching vibrations suggest that the (AsO3)3- units are not equivalent in the molecular structure of finnemanite. Two Raman bands at 383 and 399 cm-1 are assigned to the ν2 (AsO3)3- bending modes. DFT calculations enabled the position of AsO32- symmetric stretching mode at 839 cm-1, the antisymmetric stretching mode at 813 cm-1, and the deformation mode at 449 cm-1 to be calculated. Raman bands are observed at 115, 145, 162, 176, 192, 216 and 234 cm-1 as well. The two most intense bands are observed at 176 and 192 cm-1. These bands are assigned to PbCl stretching vibrations and result from transverse/ longitudinal splitting. The bands at 145 and 162 cm-1 may be assigned to Cl-Pb-Cl bending modes.

Raman spectroscopic study of the arsenite minerals leiteite ZnAs2O4 , reinerite Zn3(AsO3)2 and cafarsite Ca5(Ti,Fe,Mn)7(AsO3)12.4H2O

The selected arsenite minerals leiteite, reinerite and cafarsite have been studied by Raman spectroscopy. DFT calculations enabled the position of AsO22- symmetric stretching mode at 839 cm-1, the antisymmetric stretching mode at 813 cm-1, and the deformation mode at 449 cm-1 to be calculated. The Raman spectrum of leiteite shows bands at 804 and 763 cm-1 assigned to the As2O42- symmetric and antisymmetric stretching modes. The most intense Raman band of leiteite is the band at 457 cm-1 and is assigned to the ν2 As2O42- bending mode. A comparison of the Raman spectrum of leiteite is made with the arsenite minerals reinerite and cafarsite.

A Raman spectroscopic study of the antimonite mineral peretaite Ca(SbO)4(OH)2(SO4)2•2H2O

Raman spectra of mineral peretaite Ca(SbO)4(OH)2(SO4)2•2H2O were studied, and related to the structure of the mineral. Raman bands observed at 978 and 980 cm-1 and a series of overlapping bands observed at 1060, 1092, 1115, 1142 and 1152 cm-1 are assigned to the SO42- ν1 symmetric and ν3 antisymmetric stretching modes. Raman bands at 589 and 595 cm-1 are attributed to the SbO symmetric stretching vibrations. The low intensity Raman bands at 650 and 710 cm-1 may be attributed to SbO antisymmetric stretching modes. Raman bands at 610 cm-1 and at 417, 434 and 482 cm-1 are assigned to the SO42- 4 and 2 bending modes, respectively. Raman bands at 337 and 373 cm-1 are assigned to O-Sb-O bending modes. Multiple Raman bands for both SO42- and SbO stretching vibrations support the concept of the non-equivalence of these units in the coquandite structure.

Optical absorption, infrared, Raman and EPR spectral studies on natural Iowaite mineral

Natural iowaite, magnesium–ferric oxychloride mineral having light green color originating from Australia has been characterized by EPR, optical, IR, and Raman spectroscopy. The optical spectrum exhibits a number of electronic bands due to both Fe(III) and Mn(II) ions in iowaite. From EPR studies, the g values are calculated for Fe(III) and g and A values for Mn(II). EPR and optical absorption studies confirm that Fe(III) and Mn(II) are in distorted octahedral geometry. The bands that appear both in NIR and Raman spectra are due to the overtones and combinations of water and carbonate molecules. Thus EPR, optical, and Raman spectroscopy have proven most useful for the study of the chemistry of natural iowaite and chemical changes in the mineral.