Interpretation of the visible and near-infrared absorption spectra of compressed oxygen as collision-induced electronic transitions

1969 ◽  
Vol 47 (24) ◽  
pp. 2859-2871 ◽  
Author(s):  
G. C. Tabisz ◽  
Elizabeth J. Allin ◽  
H. L. Welsh
Keyword(s):  
Near Infrared ◽  
Low Frequency ◽  
Rotational Transition ◽  
Electronic Transitions ◽  
Absorption Bands ◽  
Specific Effects ◽  
Band Origin ◽  
Continuous Absorption ◽  
Compressed Gas ◽  
Large Width

The intensity profiles of some of the broad continuous absorption bands of oxygen in the near-infrared and visible regions were measured in the compressed gas over a range of pressures and temperatures. Three single electronic transitions (12 600, 10 600, 07620 Å) and three double transitions (6290, 5770, 4770 Å) were studied in detail. The asymmetry of the band profiles is shown to arise from a Boltzmann relation between the intensity distributions in the high and low frequency wings when the band origin is properly chosen. By assuming an appropriate rotational structure and broadening each rotational transition by a Boltzmann-modified dispersion curve the profiles of the bands could be reproduced with only minor discrepancies. These criteria, along with the well-known quadratic density dependence of the intensity, show that the bands are properly interpreted as collision-induced electronic transitions. The large width of the translational broadening functions required in the analysis indicates that the induction must be predominantly due to overlap interaction. No specific effects of (O2)2 complexes are identifiable in the spectra.

Structural, electronic and spectroscopic features of the dihydride Pd4(dppm)4(H)22+ cluster catalyst

2001 ◽  
Vol 79 (5-6) ◽  
pp. 552-559 ◽  
Author(s):  
Daniel Meilleur ◽  
Pierre D Harvey
Keyword(s):  
Low Frequency ◽  
Inert Atmosphere ◽  
Electronic Transitions ◽  
Absorption Bands ◽  
Palladium Hydride ◽  
H Nmr ◽  
Significant Difference ◽  
Simple Selection ◽  
Centrosymmetric Structure ◽  
Ft Raman

1H NMR, vibrational, and UV–vis spectroscopic measurements for Pd2(dppm)2Cl2 (dppm = Ph2PCH2PPh2), [Pd4(dppm)4(X)2](BF4)2 (X = Cl, H), and [Pd4(dmpm)4(H)2](Br)2 (dmpm = Me2PCH2PMe2) were performed to address the structure of the recently identified title cluster. Its dmpm analogue was prepared from the reaction between Pd2(dmpm)2Br2 and NaBH4 in methanol under inert atmosphere, and exhibits the expected nonet (rel. int. 1:8:28:56:70:56:28:8:1) at –5.21 ppm (in (CD3)2CO), contrasting with that of Pd4(dppm)4(H)22+ (δ + 5.15 ppm, (CD3)2CO). This significant difference is explained by the presence of the PdH residues in the deshielding region of the dppm-phenyl groups. The vibrational spectra in the low-frequency region are consistent with a centrosymmetric structure, and a scattering at 144 cm–1 in the FT-Raman spectra is observed; a peak that is assigned to ν(Pd2) on the basis of a comparison with the well established M2-bonded Pd2(dppm)2Cl2 data ((Pd2) = 149 cm–1). On the basis of the qualitative temperature behavior of the band maxima and width, the two lowest energy absorption bands in the UV–vis spectra are assigned to d σ [Formula: see text] d σ * type transition. EHMO computations predict four well-isolated frontier MO levels, defined as d σ *(Pd2)/d σ *(PdH) (LUMO + 1), d σ *(Pd2) (LUMO), d σ *(Pd2)/d σ *(PdH) (HOMO), and d σ (Pd2) (HOMO –1), and simple selection rules (u « g) indicate that only two low-energy electronic transitions are orbitally allowed, consistent with the UV–vis findings. Computer modelings show the presence of large cavities above and under the Pd4 plane, described by inner-cavity nonbonded H···H distances of ~5–8 Å.Key words: cluster, palladium, hydride, structure, spectroscopy.

Structure and microstructure of near infrared-absorbing Au–Au2S nanoparticles

2007 ◽  
Vol 22 (9) ◽  
pp. 2531-2538 ◽  
Author(s):  
Mei Chee Tan ◽  
Jackie Y. Ying ◽  
Gan Moog Chow
Keyword(s):  
Optical Properties ◽  
Surface Segregation ◽  
Near Infrared ◽  
Small Degree ◽  
Core Shell ◽  
Shell Microstructure ◽  
Absorption Bands ◽  
Interfacial Effects ◽  
Nir Absorption ◽  
Structure And Microstructure

Near infrared (NIR) absorbing nanoparticles synthesized by the reduction of HAuCl4 with Na2S exhibited absorption bands at ∼530 nm, and in the NIR region of 650–1100 nm. The NIR optical properties were not found to be related to the earlier proposed Au2S–Au core-shell microstructure in previous studies. From a detailed study of the structure and microstructure of as-synthesized particles in this work, S-containing, Au-rich, multiply-twinned nanoparticles were found to exhibit NIR absorption. They consisted of amorphous AuxS (where x = 2), mostly well mixed within crystalline Au, with a small degree of surface segregation of S. Therefore, NIR absorption was likely due to interfacial effects on particle polarization from the introduction of AuxS into Au particles, and not the dielectric confinement of plasmons associated with a core-shell microstructure.

Composition, particle size, and near-infrared irradiation effects on optical properties of Au–Au2S nanoparticles

2008 ◽  
Vol 23 (1) ◽  
pp. 281-293 ◽  
Author(s):  
Mei Chee Tan ◽  
Jackie Y. Ying ◽  
Gan Moog Chow
Keyword(s):  
Particle Size ◽  
Optical Properties ◽  
Thermal Effects ◽  
Near Infrared ◽  
Sodium Sulfide ◽  
Irradiation Effects ◽  
Absorption Bands ◽  
Molar Ratios ◽  
Nir Absorption ◽  
Structure And Microstructure

Near-infrared (NIR)-absorbing nanoparticles synthesized by the reduction of tetrachloroauric acid (HAuCl4) using sodium sulfide (Na2S) exhibited absorption bands at ∼530 nm and at the NIR region of 650−1100 nm. A detailed study on the structure and microstructure of as-synthesized nanoparticles was reported previously. The as-synthesized nanoparticles were found to consist of amorphous AuxS (x = ∼2), mostly well mixed within crystalline Au. In this work, the optical properties were tailored by varying the precursor molar ratios of HAuCl4 and Na2S. In addition, a detailed study of composition and particle-size effects on the optical properties was discussed. The change of polarizability by the introduction of S in the form of AuxS (x = ∼2) had a significant effect on NIR absorption. Also, it was found in this work that exposure of these particles to NIR irradiation using a Nd:YAG laser resulted in loss of the NIR absorption band. Thermal effects generated during NIR irradiation had led to microstructural changes that modified the optical properties of particles.

Low-frequency multiplex CARS microscopy with a high-repetition near-infrared supercontinuum laser

2021 ◽  
Author(s):  
Yusuke Arashida ◽  
Atsushi Taninaka ◽  
Takayuki Ochiai ◽  
Hiroyuki Mogi ◽  
Shoji YOSHIDA ◽  
...  
Keyword(s):  
Near Infrared ◽  
High Efficiency ◽  
Signal To Noise Ratio ◽  
Low Frequency ◽  
High Sensitivity ◽  
High Repetition ◽  
Spectrum Shaping ◽  
Crystal Phase Transition ◽  
Wavenumber Region ◽  
Anti Stokes

Abstract We have developed a multiplex Coherent anti-Stokes Raman scattering (CARS) microscope effective for low-wavenumber measurement by combining a high-repetition supercontinuum light source of 1064 nm and an infrared high-sensitivity InGaAs diode array. This system could observe the low-wavenumber region down to 55 cm-1 with high sensitivity. In addition, using spectrum shaping and spectrum modulation techniques, we simultaneously realized a wide bandwidth (<1800 cm-1), high wavenumber resolution (9 cm-1), high efficiency, and increasing signal to noise ratio by reducing the effect of the background shape in low-wavenumber region. Spatial variation of a sulfur crystal phase transition with metastable states was visualized.

Evaluation of fNIRS Signal Components Elicited by Cognitive and Hypercapnic Stimuli

2021 ◽  
Author(s):  
Pratusha Reddy ◽  
Meltem Izzetoglu ◽  
Patricia Shewokis ◽  
Michael Sangobowale ◽  
Ramon Diaz-Arrastia ◽  
...  
Keyword(s):  
Infrared Spectroscopy ◽  
Near Infrared ◽  
Low Frequency ◽  
Hemispheric Differences ◽  
Functional Versus ◽  
Functional Near Infrared Spectroscopy ◽  
Global Response ◽  
Very Low Frequency ◽  
Systemic Responses ◽  
And Task

Abstract Functional near infrared spectroscopy (fNIRS) measurements are confounded by signal components originating from multiple physiological causes, whose activities may vary temporally and spatially (across tissue layers, and regions of the cortex). Furthermore, the stimuli can induce evoked effects, which may lead to over or underestimation of the actual effect of interest. Here, we conducted a temporal, spectral, and spatial analysis of fNIRS signals collected during cognitive and hypercapnic stimuli to characterize effects of functional versus systemic responses. We utilized wavelet analysis to discriminate physiological causes and employed long and short source-detector separation (SDS) channels to differentiate tissue layers. Multi-channel measures were analyzed further to distinguish hemispheric differences. The results highlight cardiac, respiratory, myogenic, and very low frequency (VLF) activities within fNIRS signals. Regardless of stimuli, activity within VLF band had the largest contribution to the overall signal. The systemic activities dominated the measurements from the short SDS channels during cognitive stimulus, but not hypercapnic stimulus. Importantly, results indicate that characteristics of fNIRS signals vary with type of the stimuli administered as cognitive stimulus elicited variable responses between hemispheres in VLF band and task-evoked temporal effect in VLF, myogenic and respiratory bands, while hypercapnic stimulus induced a global response across both hemispheres.

Spectrophotometry of Human Hemoglobin in the near Infrared Region from 1000 to 2500 nm

1994 ◽  
Vol 2 (2) ◽  
pp. 59-65 ◽  
Author(s):  
J. Todd Kuenstner ◽  
Karl H. Norris
Keyword(s):  
Near Infrared ◽  
Infrared Region ◽  
Second Derivative ◽  
Human Hemoglobin ◽  
Absorption Bands ◽  
Near Infrared Region ◽  
Absorbance Spectra

Absorbance and first and second derivative absorbance spectra and quarter-millimolar absorptivity coefficients for hemoglobin species including oxy-, deoxy-, carboxy- and methemoglobin in the visible and in the near infrared regions from 620 nm to 2500 nm are presented. At wavelengths longer than 1500 nm, the absorbance and second derivative absorbance spectra of hemoglobin species are similar for all of the species. Absorption bands are present centred at 1690, 1740, 2056, 2170, 2290 and 2350 nm.

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