ORCID Profile
0000-0003-4346-4457
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Research Topics
In Research Link Australia (RLA), "Research Topics" refer to ANZSRC FOR and SEO codes. These topics are either sourced from ANZSRC FOR and SEO codes listed in researchers' related grants or generated by a large language model (LLM) based on their publications.
Top 5 Research Topics
ANZSRC Field of Research (FoR)
Physical Chemistry (Incl. Structural) | Chemical Spectroscopy | Physical Chemistry of Materials | Characterisation Of Macromolecules | Nanochemistry and Supramolecular Chemistry | Quantum Chemistry | Structural Chemistry and Spectroscopy | Supramolecular Chemistry | Structural Chemistry | Biological And Medical Chemistry | Physical Chemistry not elsewhere classified | Nanotechnology | Group Theory And Generalisations (Incl. Topological Groups And Lie | Nanoscale Characterisation | Nanobiotechnology | Atomic and Molecular Physics
ANZSRC Socio-Economic Objective (SEO)
Chemical sciences | Expanding Knowledge in the Chemical Sciences | Expanding Knowledge in the Physical Sciences | Infectious diseases | Human Diagnostics | Medical instrumentation | Physical sciences |
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Publications
Thermodynamically Favored Anion Rearrangements in Li and Na Complexes of (S)-N-α-(Methylbenzyl)allylamine
Publisher: American Chemical Society (ACS)
Date: 27-02-2009
DOI: 10.1021/OM801165E
Computational Infrared Spectroscopy of 958 Phosphorus-Bearing Molecules
Publisher: Frontiers Media SA
Date: 08-04-2021
DOI: 10.3389/FSPAS.2021.639068
Abstract: Phosphine is now well-established as a biosignature, which has risen to prominence with its recent tentative detection on Venus. To follow up this discovery and related future exoplanet biosignature detections, it is important to spectroscopically detect the presence of phosphorus-bearing atmospheric molecules that could be involved in the chemical networks producing, destroying or reacting with phosphine. We start by enumerating phosphorus-bearing molecules (P-molecules) that could potentially be detected spectroscopically in planetary atmospheres and collecting all available spectral data. Gaseous P-molecules are rare, with speciation information scarce. Very few molecules have high accuracy spectral data from experiment or theory instead, the best current spectral data was obtained using a high-throughput computational algorithm, RASCALL, relying on functional group theory to efficiently produce approximate spectral data for arbitrary molecules based on their component functional groups. Here, we present a high-throughput approach utilizing established computational quantum chemistry methods (CQC) to produce a database of approximate infrared spectra for 958 P-molecules. These data are of interest for astronomy and astrochemistry (importantly identifying potential ambiguities in molecular assignments), improving RASCALL's underlying data, big data spectral analysis and future machine learning applications. However, this data will probably not be sufficiently accurate for secure experimental detections of specific molecules within complex gaseous mixtures in laboratory or astronomy settings. We chose the strongly performing harmonic ωB97X-D/def2-SVPD model chemistry for all molecules and test the more sophisticated and time-consuming GVPT2 anharmonic model chemistry for 250 smaller molecules. Limitations to our automated approach, particularly for the less robust GVPT2 method, are considered along with pathways to future improvements. Our CQC calculations significantly improve on existing RASCALL data by providing quantitative intensities, new data in the fingerprint region (crucial for molecular identification) and higher frequency regions (overtones, combination bands), and improved data for fundamental transitions based on the specific chemical environment. As the spectroscopy of most P-molecules have never been studied outside RASCALL and this approach, the new data in this paper is the most accurate spectral data available for most P-molecules and represent a significant advance in the understanding of the spectroscopic behavior of these molecules.
Infrared spectroscopy of ozone and hydrogen chloride aerosols
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B905424N
Abstract: Aerosols of ozone have been generated in a collisional cooling cell and observed over a small temperature range via FTIR spectroscopy, with the phase transition from the vapour taking place in the range 80-84 K. The condensed phase bands at 1038 cm(-1) (nu3) and 2105 cm(-1) (nu1+nu3) were assigned to the liquid phase. Aerosols were also generated from mixtures of ozone and HCl. In the presence of liquid ozone aerosols, evidence of solvated HCl was observed via a broad IR band 2795 cm(-1). Notably, production of a metastable, amorphous solid phase of HCl (exhibiting a narrow band at 2780 cm(-1)) was favoured to the extent that it could be generated in large excess over the crystalline orthorhombic form that usually dominates at 80 K.
Reading between the lines: Exposing underlying features of high resolution infrared spectra (CHC1F2 )
Publisher: Royal Society of Chemistry (RSC)
Date: 2003
DOI: 10.1039/B300689A
Tetrafluoroethylene: High resolution FTIR spectroscopy
Publisher: Royal Society of Chemistry (RSC)
Date: 2002
DOI: 10.1039/B207405B
Halocarbons as hydrogen bond acceptors: a spectroscopic study of haloethylbenzenes (PhCH2CH2X, X = F, Cl, Br) and their hydrate clusters
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C7CP07365H
Abstract: The hydrogen bond acceptor strength of a series of halocarbons is studied by electronic and vibrational spectroscopy.
A sting in the tail of flexible molecules: Spectroscopic and energetic challenges in the case of p-aminophenethylamine
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2CP40828G
Abstract: The neurotransmitter analogue p-aminophenethylamine (APEA) illustrates many of the pitfalls and challenges associated with spectroscopic and conformational analysis of flexible molecules. The combined experimental-theoretical study presented here resolves a long-standing controversy over its conformational energetic preferences. Jet-cooled resonance enhanced two-photon ionisation (R2PI) and IR-UV ion depletion techniques enabled conformer-specific IR spectra in the NH-CH stretch region to be measured for four distinct conformers of APEA. Comparison of spectra with theoretical calculations (including MP2, M06-2X and B3LYP with aug-cc-pVTZ basis sets) allows the two most populated conformers to be unambiguously identified as those having a gauche arrangement of the side chain, which facilitates an NH···π type hydrogen bond. The other two observed conformers are assigned to structures with an anti-side chain. A fifth gauche conformer, predicted to be least stable, is not observed. Comparison with published conformer specific IR spectra of tyramine (Makara et al., J. Phys. Chem. A, 2008, 112, 13463-13469) and Raman spectra of phenylethylamine (Golan et al., J. Chem. Phys., 2009, 131, 024305) reveals an entirely consistent pattern of spectral signatures associated with the four specific conformations of the ethylamine side chain evident in APEA, and aids assignment of the associated CH and NH stretch fundamentals, some of which have very weak IR intensities. Extensive calculations of the relative energetic trends of the five conformers have been carried out. In comparison to the highest level of theory considered, CCSD(T)-F12b/cc-pVDZ-F12, MP2 overestimate the energy difference, whereas DFT significantly underestimates the energetic preference for NH···π stabilised gauche conformers, although inclusion of dispersion (M06-2X, B3LYP-D3) improves the DFT results.
Surface-enhanced raman scattering spectroscopy of resveratrol
Publisher: CSIRO Publishing
Date: 2008
DOI: 10.1071/CH08204
Abstract: We report here, for the first time, the surface-enhanced Raman scattering (SERS) spectra of resveratrol using KNO3-aggregated citrate-reduced silver (Ag) colloids. The technique provided a substantial spectral enhancement and therefore good quality spectra of resveratrol at parts per million (ppm) concentrations. The detection limit was found to be μM, equivalent to .2 ppm. The SERS profile additionally closely resembled its normal solid-state Raman spectrum with some changes in relative intensity. These intensity changes, together with a precise band assignment aided by density functional theory calculations at the B3LYP/6–31G(d) level, allowed the determination of the structural orientation of the adsorbed resveratrol on the surface of the metal nanoparticles. In particular, the SERS spectra obtained at different resveratrol concentrations exhibited concentration-dependent features, suggesting an influence of surface coverage on the orientation of the adsorbed molecules. At a high concentration, an adoption of close-to-upright orientation of resveratrol adsorbed on the metal surface through the p-OH phenyl ring is favoured. The binding structure is, however, altered at lower surface coverage when the concentration decreases to a tilted orientation with the trans-olefin C=C bond aligning closer to parallel to the surface of the Ag nanoparticles.
Grape phylloxera (Daktulosphaira vitifoliae) – a review of potential detection and alternative management options
Publisher: Wiley
Date: 02-08-2012
The prediction of far-infrared spectra for molecular crystals of forensic interest – Phenylethylamine, ephedrine & pseudoephedrine
Publisher: Elsevier BV
Date: 03-2020
Terahertz and Mid-infrared Spectra of Cold Formic Acid Aerosol Particles
Publisher: American Chemical Society (ACS)
Date: 20-08-2018
IR spectroscopy of physical and chemical transformations in cold hydrogen chloride and ammonia aerosols
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B905425C
Abstract: Aerosol particles of hydrogen chloride corresponding to three distinct solid phases have been generated in a collisional cooling cell and observed via FTIR spectroscopy. The cubic phase of HCl was observed with cell temperatures of 90-100 K, while the highly ordered orthorhombic phase predominated below this temperature. The previously reported metastable phase was also observed under some conditions. Density functional theory calculations at the B3LYP/6-311+G(d,p) level were performed on HCl clusters with a planar, zig-zag arrangement. Computed IR spectra for chain lengths up to 15 converge to show a band shape that is characteristic of the orthorhombic HCl phase. Injection of water along with HCl was found to have little influence on the formation of HCl particles. The reaction between HCl and NH3 to produce NH4Cl particles was also examined and found to occur over a wide range of temperatures (80-300 K). The formation of homogenous particles of HCl and NH3 competed with this chemical reaction as the cell temperature was lowered and when higher pressures of N2 buffer gas were used.
Density functional theory for prediction of far-infrared vibrational frequencies: molecular crystals of astrophysical interest
Publisher: Oxford University Press (OUP)
Date: 13-07-2017
Completing the picture in the rovibrational analysis of chlorodifluoromethane (CHCIF2 ): V3 and v8
Publisher: Informa UK Limited
Date: 08-2004
Thiols as Hydrogen Bond Acceptors and Donors: Spectroscopy of 2-Phenylethanethiol Complexes
Publisher: American Chemical Society (ACS)
Date: 16-08-2018
Abstract: Evidence and understanding of sulfur-centered hydrogen bonding, especially where the donor is a thiol, lags far behind that for conventional OH interactions. To help address this deficiency, conformer specific IR spectra of 2-phenylethanethiol (PET) and associated 1:1 solvent complexes have been measured in SH, OH, and CH stretch regions using resonant-two-photon-ionization (R2PI) and IR-UV ion dip spectroscopic techniques. The aromatic and aliphatic CH stretch regions show signature differences between anti and gauche conformers. Supported by ab initio calculations, a PET-water cluster with an OH···S arrangement and a PET-diethyl ether cluster expressing an SH···O interaction were identified. The SH stretch band of the SH···O complex is red-shifted and undergoes significant intensity enhancement compared to the bare molecule, which is characteristic of hydrogen bonding. These findings offer insight into the nature of the thiol functional group as a potential hydrogen bond donor and acceptor.
Structure determination of sec-butylbenzene rotamers by UV spectroscopy and ab initio calculations
Publisher: Elsevier BV
Date: 09-2008
High resolution far infrared spectroscopy of HFC-134a using a collisional cooling cell adapted to a synchrotron source
Publisher: Elsevier BV
Date: 08-2015
Interplanar torsion in the S1 ←S0 electronic spectrum of jet cooled 1-phenylimidazole
Publisher: AIP Publishing
Date: 13-12-2004
DOI: 10.1063/1.1822922
Abstract: The S1←S0 transition of 1-phenylimidazole (1PI) has been studied in a supersonic jet expansion by resonant two-photon ionization. The origin band at 36 075 cm−1 is accompanied by a low frequency progression associated with torsion about the bond connecting phenyl and imidazole groups. Torsional potentials have been determined for both states. In S0, φmin=37.2±0.5° and the planar barrier is 339±20 cm−1, while in S1, φmin=17.6±0.5° and the planar barrier is 57±2 cm−1. The transition moment alignment is observed to be consistent with an excited state of Lb character, in spite of the “off-axis” conjugation provided by the imidazole ring. These results are compared with ab initio calculations on both states, performed using Hartree–Fock, Møller–Plesset second-order perturbation, density functional theory with the Becke3–Lee–Yang–Parr functional, time-dependant density functional theory, configuration interaction singles, and complete active space self-consistent field methods. Solution-phase UV spectra of neutral and protonated 1PI are also reported.
High resolution FTIR spectroscopy of 1,1,1,2-tetrafluoroethane: v6
Publisher: Elsevier BV
Date: 03-2003
IR Band Profiling of Dichlorodifluoromethane in the Greenhouse Window: High-Resolution FTIR Spectroscopy of ν2 and ν8
Publisher: American Chemical Society (ACS)
Date: 25-03-2014
DOI: 10.1021/JP501302Q
Abstract: The IR spectrum of dichlorodifluoromethane (i.e., R12 or Freon-12) is central to its role as a major greenhouse contributor. In this study, high-resolution (0.000 96 cm(-1)) Fourier transform infrared spectra have been measured for R12 s les either cooled to around 150 K or at ambient temperature using facilities on the infrared beamline of the Australian Synchrotron. Over 14,000 lines of C(35)Cl2F2 and C(35)Cl(37)ClF2 were assigned to the b-type ν2 band centered around 668 cm(-1). For the c-type ν8 band at 1161 cm(-1), over 10,000 lines were assigned to the two isotopologues. Rovibrational fits resulted in upper state constants for all these band systems. Localized avoided crossings in the ν8 system of C(35)Cl2F2, resulting from both a direct b-axis Coriolis interaction with ν3 + ν4 + ν7 and an indirect interaction with ν3 + ν4 + ν9, were treated. An improved set of ground state constants for C(35)Cl(37)ClF2 was obtained by a combined fit of IR ground state combination differences and previously published millimeter wave lines. Together these new sets of constants allow for accurate prediction of these bands and direct comparison with satellite data to enable accurate quantification.
The rotational spectrum of propynal in the 250–700 GHz range using coherent synchrotron radiation Fourier transform spectrometry
Publisher: Elsevier BV
Date: 2015
Nitriles as directionally tolerant hydrogen bond acceptors: IR-UV ion depletion spectroscopy of benzenepropanenitrile and its hydrate clusters
Publisher: Elsevier BV
Date: 09-2016
Infrared characterisation of acetonitrile and propionitrile aerosols under Titan's atmospheric conditions
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C6CP08110J
Abstract: Acetonitrile and propionitrile aerosols were generated under simulated Titan conditions where new insight into the ice morphology, particle size and formation/diffusion kinetics has been extracted by online infrared spectroscopy.
The far-infrared rotational spectrum of ethylene oxide
Publisher: American Astronomical Society
Date: 11-06-2012
NUCLEAR MAGNETIC RESONANCE METABOLIC PROFILING OF LEAVES FROM VITIS VINIFERA INFESTED WITH ROOT-FEEDING GRAPE PHYLLOXERA (DAKTULOSPHAIRA VITIFOLIAE FITCH) UNDER FIELD CONDITIONS
Publisher: International Society for Horticultural Science (ISHS)
Date: 07-2014
EARLY DETECTION OF GRAPE PHYLLOXERA (DAKTULOSPHAIRA VITIFOLIAE FITCH) INFESTATION THROUGH IDENTIFICATION OF CHEMICAL BIOMARKERS
Publisher: International Society for Horticultural Science (ISHS)
Date: 08-2011
High resolution FTIR spectroscopy of the v1 band of NSCI
Publisher: Royal Society of Chemistry (RSC)
Date: 2005
DOI: 10.1039/B416215C
Conformer Specific Ultraviolet and Infrared Detection of Nicotine in the Vapor Phase
Publisher: American Chemical Society (ACS)
Date: 23-10-2019
Abstract: A gas-phase electronic spectrum of nicotine in a supersonic expansion has been recorded using two-color resonant two-photon ionization spectroscopy. Efficient photoionization was achievable only via the pyridine chromophore owing to poor Franck-Condon overlap in the
High resolution synchrotron FTIR spectroscopy of the far infrared ν10 and ν11 bands of R152a (CH3 CHF2 )
Publisher: Elsevier BV
Date: 11-2008
Conformational Polymorphism in N‐(4′‐methoxyphenyl)‐ 3‐bromothiobenzamide
Publisher: Wiley
Date: 26-03-2007
Abstract: Three conformational polymorphs of N-(4'-methoxyphenyl)-3-bromothiobenzamide, yellow alpha, orange beta, and yellow gamma, have been identified by single-crystal X-ray diffraction. The properties and structure of the polymorphs were examined with FT Raman, FTIR (ATR), and UV/Vis spectroscopy, as well as differential scanning calorimetry. Computational data on rotational barriers in the isolated gas-phase molecule indicate that the molecular conformation found in the alpha form is energetically preferred, but only by around 2 kJ mol(-1) over the gamma conformation. The planar molecular structure found in the beta form is destabilized by 10-14 kJ mol(-1), depending on the calculation method. However, experimental evidence suggests that the beta polymorph is the most stable crystalline phase at room temperature. This is attributed to the relative planarity of this structure, which allows more and stronger intermolecular interactions, that is, more energetically effective packing. Calculated electronic-absorption maxima were in agreement with experimental spectra.
High-resolution Fourier-transform infrared spectroscopy of the V6 and Coriolis perturbation allowed V10 modes of ketenimine
Publisher: AIP Publishing
Date: 09-12-2011
DOI: 10.1063/1.3664624
Abstract: High-resolution FTIR spectra of the short lived species ketenimine have been recorded in the region 700–1300 cm−1 and over 1500 transitions of the ν10 and ν6 modes have been assigned. Effective rotational and centrifugal distortion parameters for the v10 = 1 and v6 = 1 (excluding Ka = 5) states were determined by co-fitting transitions, and treating strong a- and c-axis Coriolis interactions between them. Other perturbations attributed to interactions with the v8 = 2 and v12 = 1 + v8 = 1 dark-states were also observed and treated. The ν10 transitions are predicted to be inherently very weak, but are enhanced by an intensity stealing effect with the highly IR active ν6 mode. A mechanism for this intensity stealing in ketenimine is also detailed.
Spectral curve fitting of dielectric constants
Publisher: AIP Publishing
Date: 2017
DOI: 10.1063/1.4975398
Abstract: Optical constants are important properties governing the response of a material to incident light. It follows that they are often extracted from spectra measured by absorbance, transmittance or reflectance. One convenient method to obtain optical constants is by curve fitting. Here, model curves should satisfy Kramer-Kronig relations, and preferably can be expressed in closed form or easily calculable. In this study we use dielectric constants of three different molecular ices in the infrared region to evaluate four different model curves that are generally used for fitting optical constants: (1) the classical d ed harmonic oscillator, (2) Voigt line shape, (3) Fourier series, and (4) the Triangular basis. Among these, only the classical d ed harmonic oscillator model strictly satisfies the Kramer-Kronig relation. If considering the trade-off between accuracy and speed, Fourier series fitting is the best option when spectral bands are broad while for narrow peaks the classical d ed harmonic oscillator and the Triangular basis fitting model are the best choice.
Coordination and Reduction of HMPA in the Lithiation of (S)‐N‐(α‐Methylbenzyl)allylamine: Crystal Structures of {(S)‐α‐[PhC(H)CH3](CH2CH=CH2)NLi·H
Publisher: Wiley
Date: 07-2006
Abstract: Monolithiation of the chiral amine ( S )‐ N ‐(α‐methylbenzyl)allylamine, in the presence of the strong Lewis donor solvent hexamethylphoshoramide (HMPA), results in pale yellow crystals which have been crystallographically analysed revealing the structure of the complex to be an asymmetric cisoid dimer {( S )‐α‐[PhC(H)CH 3 ](CH 2 CH=CH 2 )NLi · HMPA} 2 . Variable‐temperature NMR studies show this complex can undergo a thermally induced rearrangement to a 1‐azaallyl complex at ca. 90 °C. Attempted dilithiation of the chiral amine at the N and vinylic C centres with n BuLi and HMPA results in competitive reduction of HMPA to give crystals of the lithium dimethylamidophosphite, structurally authenticated as the hexamer [(Me 2 N) 2 POLi] 6 , in which the Li cation is bonded preferentially to the O centre and not P. The effect is a reduction in the oxidation state of the P centre from (V) to (III), which is supported by ab initio calculations showing the crystal structure to represent the most thermodynamically stable of the possible isomers. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Synchrotron Far-Infrared Spectra for the Characterisation of Molecular Crystals of Forensic Interest: Amphetamine, Methamphetamine, MDA, MDMA and Substituted Methcathinones
Publisher: Elsevier BV
Date: 09-2020
The prediction of far-infrared spectra for planetary nitrile ices using periodic density functional theory with comparison to thin film experiments
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8CP04219E
Abstract: The application of high accuracy periodic DFT calculations to replicate laboratory thin film spectra allowing the assignment of vibrational far-infrared modes in nitrile-bearing planetary ices.
Ro-vibrational analysis of the ν9 and ν16 bands of R152a
Publisher: Elsevier BV
Date: 09-2008
High-resolution FTIR spectroscopy of HNSO—Analysis of the highly perturbed ν4, ν6 and 2ν5 bands
Publisher: Elsevier BV
Date: 12-2006
Analysis of 5-hydroxyisoflavones by surface-enhanced raman spectroscopy: Genistein and methoxy derivatives
Publisher: American Chemical Society (ACS)
Date: 07-11-2011
DOI: 10.1021/JP207730G
Abstract: A series of 5-hydroxy-isoflavones-genistein, biochanin A, prunetin, and 4',7-dimethoxygenistein-have been studied by surface-enhanced Raman spectroscopy (SERS). Citrate reduced silver colloids were employed as a standard technique to measure SER spectra over a range of pH and concentrations. Density functional theory calculations were used to assist in determining the mode of interaction of isoflavones with the silver nanoparticles. It is revealed that biochanin A and prunetin interact with the silver nanoparticles upon deprotonation of the 7- and the 4'-OH groups, respectively, to show SERS activity. Correlations of their spectra with SERS of genistein strongly support the presence of multiple interaction modes involving both of the OH groups in genistein, in a similar manner to daidzein. Surprisingly, however, under these conditions, the 5-OH group was found to be noninteractive as revealed by attempts to measure SERS of 4',7-dimethoxygenistein. This was attributed partly to the low solubility and, more importantly, to the influence of steric hindrance, caused by the position of the pendant phenyl ring, which prevented interaction with the Ag colloid surface. These results complement recent work on daidzein and formononetin and provide further insight into understanding the SER spectra of isoflavones.
Resonant 2-photon ionization study of the conformation and the binding of water molecules to 2-phenylethanethiol (PhC H2 C H2 SH)
Publisher: AIP Publishing
Date: 22-04-2008
DOI: 10.1063/1.2903477
Abstract: The structures of 2-phenylethanethiol (PET, PhCH2CH2SH) and its 1:1 water clusters have been studied using resonant two-photon ionization spectroscopy including band contour analysis and UV-UV holeburning, combined with extensive ab initio calculations on ground and excited states. The most populated conformer, labeled Ggπ, has a gauche arrangement about the SCCC and HSCC bonds that permits a stabilizing SH⋯π type of hydrogen bond. The other observed conformer, Ag, is anti with respect to the SCCC bond. In the dominant 1:1 water cluster, a water molecule binds to the Ggπ conformer via an OH⋯S hydrogen bond and two significant CH⋯O interactions. There is also evidence for water binding to conformer Ag with a similar arrangement, and for a second Ggπ cluster where water inserts between the SH and the aromatic ring. The additional interactions to the water molecules result in net De binding energies approximately double those resulting from a single thiol-water hydrogen bond. The (π,π*)1 excited state lifetimes in the bare molecules are very short because of internal conversion to a dissociative (n,π*)1 state related to the thiol. In the dominant Gw1 cluster, the lifetime is significantly increased from & to∼4ns. Hydrogen bonding to the thiol, which raises the energy of the dissociative (n,π*)1 state, accounts for this behavior.
Vibrational Anharmonicities and Reactivity of Tetrafluoroethylene
Publisher: American Chemical Society (ACS)
Date: 15-07-2014
DOI: 10.1021/JP500811W
Coordination and Reduction of HMPA in the Lithiation of (S)‐N‐(α‐Methylbenzyl)allylamine: Crystal Structures of {(S)‐α‐[PhC(H)CH3](CH2CH=CH2)NLi·H
Publisher: Wiley
Date: 10-2008
High resolution FTIR spectroscopy of pentafluoroethane: Perturbations in the Coriolis doublet of v4 and v13
Publisher: Elsevier BV
Date: 04-2005
A spectroscopic study of nicotine analogue 2-phenylpyrrolidine (PPD) using resonant two-photon ionization (R2PI), microwave, and 2D NMR techniques
Publisher: American Chemical Society (ACS)
Date: 04-02-2009
DOI: 10.1021/JA807995N
Abstract: Conformational preferences of the nicotine analogue 2-phenylpyrrolidine (PPD) have been studied in both gaseous and solution phases. Theoretical calculations at the MP2 and B3LYP levels point to 5-6 stable conformers which differ in three degrees of conformational freedom torsion between the two rings, inversion at the pyrrolidine (PY) amine, and PY ring puckering, characterized using the Cremer-Pople definition for pseudorotation. Only one conformer has a trans arrangement between the amino hydrogen and the phenyl substituent. It is 6-8 kJ mol(-1) more stable than the cis conformers, has a perpendicular ring arrangement, and puckers at the nitrogen atom--similar to structures reported for nicotine. Resonant two-photon ionization (R2PI) data, including hole burn spectra, indicate only one conformer is present in the free jet expansion, and band contour analysis suggests assignment to the trans conformer. Confirmation was provided by microwave spectroscopy. Fifty-seven lines measured in the 48-72 GHz region were assigned to 206 b-type transitions and fitted to yield rotational constants within 2 MHz of MP2 values predicted for the trans conformer. The solution-phase conformers of PPD were studied using 1D and 2D (1)H NMR spectroscopy and solvent-based theoretical calculations. In marked contrast to the gas phase, NMR data reveals only cis conformers present in solution. Calculations confirm increased stability for these conformers when placed in simulated chloroform or water environments. Solvent molecules are believed to disrupt a crucial N...H(ortho) stabilizing interaction present within the trans conformer.
Structural, vibrational, and rovibrational analysis of tetrafluoroethylene
Publisher: AIP Publishing
Date: 03-12-2012
DOI: 10.1063/1.4768417
Abstract: High resolution FTIR spectra of 13C enriched tetrafluoroethylene (C2F4) were measured at 150 K at the Australian Synchrotron. Rovibrational transitions were assigned in the a-type symmetric and b-type antisymmetric CF2 stretches of 12C13CF4 and 13C2F4 near 1170 cm−1 and 1300 cm−1, respectively. Ground vibrational state spectroscopic constants for both molecules were determined in addition to the upper state constants for ν11 and ν9 of 13C2F4 and ν11, ν2+ν6, and ν5 of 12C13CF4. The ground state constants, along with those determined for the 12C2F4 isotopologue from previously published data, were used to determine a semi-experimental re structure rCC = 132.36 ± 0.37 pm, rCF = 131.11 ± 0.23 pm, αFCC = 123.3 ± 0.3° in excellent agreement with ab initio structures. Lower resolution FTIR spectra were measured between 100 and 5000 cm−1 at room temperature and band centres obtained for all modes of the three isotopologues although only 5 out of 12 modes in 12C2F4 and 13C2F4 are infrared (IR) active, the others were inferred from combination and hot-band positions. A number of modes are observed to be infrared active only in the 12C13CF4 isotopologue due to its lower symmetry. Most notably, decoupling of the antisymmetric CF2 motions in the two halves of 12C13CF4 results in 2 strongly IR active modes that involve motion at one carbon or the other.
Size and temperature dependence in the far-IR spectra of water ice particles
Publisher: American Astronomical Society
Date: 20-09-2012
High-resolution FTIR spectroscopy of the nu(8) and Coriolis perturbation allowed nu(12) bands of ketenimine
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C0CP01816C
Abstract: High resolution FTIR spectra have been recorded in the region 250-770 cm(-1) using synchrotron radiation and over 2000 transitions to the ν(8) and ν(12) states of the short lived species ketenimine have been assigned. Ground state combination differences combined with published microwave transitions were used to refine the constants for the ground vibrational state. Rotational and centrifugal distortion parameters for the v(8) = 1 and v(12) = 1 levels were determined by co-fitting transitions, and treating a strong a-axis Coriolis interaction. Selection rules for the observed ν(12) transitions indicate that they arise solely from "perturbation allowed" intensity resulting from this Coriolis interaction.
Binary-Phase Acetonitrile and Water Aerosols: Infrared Studies and Theoretical Simulation at Titan Atmosphere Conditions
Publisher: American Chemical Society (ACS)
Date: 11-07-2018
Comparative analysis of surface-enhanced Raman spectroscopy of daidzein and formononetin
Publisher: American Chemical Society (ACS)
Date: 05-05-2010
DOI: 10.1021/JP101389T
Abstract: Phytoestrogens daidzein (4',7-dihydroxy-isoflavone) and formononetin (4'-methoxy-7-hydroxy-isoflavone) have been studied by surface-enhanced Raman (SER) spectroscopy. Spectra were acquired in the presence of citrate-reduced silver colloids, over a range of pH and concentrations. Density functional theory calculations were used to assist assignment of the normal Raman spectra and help determine the mode of interaction of isoflavones with the silver nanoparticles. Formononetin does not show SER activity unless the 7-OH group is deprotonated, and accordingly, the interaction with the silver surface occurs via the deprotonated site. Daidzein, on the other hand, appears to contain multiple species at the surface, interacting via both the hydroxyl groups at 7-OH and 4'-OH, after deprotonation. This is an important result that points to potential future SERS applications in phytoestrogen analysis and provides a foundation for understanding the SER spectra of isoflavones.
Surface‐enhanced Raman spectroscopic analysis of fonofos pesticide adsorbed on silver and gold nanoparticles
Publisher: Wiley
Date: 26-01-2010
DOI: 10.1002/JRS.2579
Overview of high-resolution infrared measurement and analysis for atmospheric monitoring of halocarbons
Publisher: American Chemical Society (ACS)
Date: 19-08-2010
DOI: 10.1021/AC101425D
Abstract: The current state of the art in recording and analyzing rotationally resolved vibration-rotation bands of atmospheric pollutant halocarbon species is reviewed. It is shown that in order to obtain molecular constants of sufficient accuracy to simulate the vibration-rotation structure over the range of atmospheric temperatures, it is necessary to obtain spectra at a range of temperatures using static cooling cells, supersonic jet expansions, and collisional cooling devices employ sophisticated pattern recognition and analysis software assign and fit spectral perturbations and use spectral simulation and digital spectral subtraction (SASSI) to further simplify spectral bands for analysis. To demonstrate the techniques, an analysis of the ν(5) band of CH(37)ClF(2) in natural abundance is presented.
An improved model for malaria pigment and β‐hematin: Fe(OEP)picrate
Publisher: Wiley
Date: 16-08-2017
DOI: 10.1002/JRS.5176
Decongestion of high-resolution FTIR-spectra and assignment of CHF2CF3
Publisher: Elsevier BV
Date: 10-2004
High-resolution FTIR spectroscopy of chlorodifluoromethane: v2 and v7
Publisher: Elsevier BV
Date: 06-2002
The Limits of Rovibrational Analysis: The Severely Entangled ν1 Polyad Vibration of Dichlorodifluoromethane in the Greenhouse IR Window
Publisher: American Chemical Society (ACS)
Date: 06-11-2014
DOI: 10.1021/JP5087784
Abstract: Five intense bands of dichlorodifluoromethane (CFC-12, or R12) in the infrared atmospheric window help make it a major greenhouse contributor. These include the ν1 fundamental at 1101.4 cm(-1) and the ν2 + ν3 combination at 1128.6 cm(-1). High-resolution spectra measured using the Australian Synchrotron Far-Infrared beamline were analyzed, and transitions of C(35)Cl2F2 were assigned to ν1, ν2 + ν3, and the ν3 + 2ν5 combination at 1099.7 cm(-1). The (v3 = 1 v5 = 2) state couples indirectly to v1 = 1 via Fermi resonances linking both states with v2 = v3 = 1. The v1 = 1 rotational levels are further riddled with perturbations and avoided crossings due to Coriolis resonance with the upper vibrational states of ν2 + ν9 at 1102.4 cm(-1) and (indirectly) ν2 + ν7 at 1105.8 cm(-1). A global treatment of all these states fits the observed line positions and satisfactorily accounts for the significant intensity of ν2 + ν3. Spectral simulations elucidate resonance perturbations that affect the distribution of IR absorption in the CF stretch region, and consequently the global warming potential of R12. Combination levels derived from rovibrational analysis lead to reassessment of the gas phase wavenumber values for the ν3 (458.6 cm(-1)), ν7 (437.7 cm(-1)) and ν9 (436.9 cm(-1)) fundamentals of C(35)Cl2F2, consistent with a cold, vapor phase far IR spectrum and previously published solid state spectra. B3LYP and MP2 anharmonic frequency calculations provide further support. At the MP2/aug-cc-pVTZ level, the root mean square (r.m.s.) error for unscaled anharmonic fundamentals is 6.2 cm(-1), decreased to 1.7 cm(-1) if only considering the seven lowest wavenumber modes, and integrated band intensities according with experimental literature values. Smaller basis sets produce band strengths that are too high. Low-resolution band assignments are reported for C(35)Cl(37)ClF2, C(37)Cl2F2, and (13)C(35)Cl2F2.
High-resolution Fourier-transform infrared spectroscopy of the Coriolis coupled ground state and nu(7) mode of ketenimine
Publisher: AIP Publishing
Date: 16-06-2011
DOI: 10.1063/1.3597775
Abstract: High resolution FTIR spectra of the short lived species ketenimine have been recorded in the regions 390–1300 cm−1 and 20–110 cm−1 using synchrotron radiation. Two thousand six hundred sixty transitions of the ν7 band centered at 693 cm−1 and 126 far-IR rotational transitions have been assigned. Rotational and centrifugal distortion parameters for the ν7 mode were determined and local Fermi and b-axis Coriolis interactions with 2ν12 are treated. A further refinement of the ground state, ν12 and ν8 parameters was also achieved, including the treatment of previously unrecognized ac-axis and ab-axis second order perturbations to the ground state.
Water ice nanoparticles: size and temperature effects on the mid-infrared spectrum
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C3CP43974G
Abstract: Mid-infrared spectra have been measured for cubic ice (I(c)) nanoparticles (3-150 nm diameter) formed by rapid collisional cooling over a wide range of temperatures (5-209 K). Spectral diagnostics, such as the ratio of surface related dangling OH to interior H-bonded OH stretch bands, reveal the manner in which particle size depends on bath gas temperature and density, and on water molecule concentration. For particles smaller than 5 nm strained intermolecular bonds on the surface and subsurface cause the predominant OH stretch peak position to be dramatically blue shifted by up to 40 cm(-1). In the size regime of 8-200 nm the position of the OH stretch absorption band maximum is relatively unaffected by particle size and it is possible to measure the temperature dependence of the peak location without influences from the surface or scattering. The band maximum shifts in a linear fashion from 3218 cm(-1) at 30 K to 3253 cm(-1) at 209 K, which may assist with temperature profiling of ice particles in atmospheric clouds and extraterrestrial systems. Over the same temperature range the librational mode band shifts very little, from 870 to 860 cm(-1). In the water stretching and bending regions discrete spectral features associated with the surface or sub-surface layers have been detected in particles as large as 80 nm.
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