Biomedical subjects

P Thaddeus

Publications and source records attributed to P Thaddeus.

At least 19 recordsLinked to original sources

PubMed2006

The prebiotic molecules observed in the interstellar gas.

Over 130 molecules have been identified in the interstellar gas and circumstellar shells, the largest among them is a carbon chain with 13 atoms and molecular weight of 147 (twice that of the simplest amino acid glycine). The high reliability of astronomical identifications, as well as the fairly accurate quantitative analysis which can often be achieved, is emphasized. Glycine itself has been claimed, but a recent analysis indicates that few, if any, of the astronomical radio lines attributed to glycine are actually from that molecule. Polycyclic aromatic hydrocarbons (PAHs) have long been proposed as the source of the unidentified infrared bands between 3 and 16 microm, but no single PAH has been identified in space, partly because PAHs generally have weak or non-existent radio spectra. A remarkable exception is the non-planar corannulene molecule (C20H10) that has a strong radio spectrum; in the rich molecular cloud TMC-1, it is found that less than 10-5 of the carbon is contained in this molecule, suggesting that PAHs are not the dominant large molecules in the interstellar gas, as has been claimed. Owing to inherent spectroscopic limitations, determining the structures of the large molecules in space may require capture of the dust grains, which are continually entering the outer Solar System.

Evolution, Chemical↗

PubMed2006

Detection of low-frequency lambda-doublet transitions of the free 12CH and 13CH radicals.

By Fourier transform microwave spectroscopy, lambda-doubling transitions of (12)CH and (13)CH in the lowest rotational levels of the X(2) product operator(1/2) ground state have been directly detected, which has not been done previously. For both radicals, hyperfine-split lines have been measured to an accuracy of better than 1 ppm between 3 and 15 GHz, an improvement of at least 2 orders of magnitude over previous laboratory data. The measured frequencies have been combined with all previous data for CH and (13)CH in the v = 0 level of the X(2) product operator electronic state to determine improved hyperfine parameters. The production of CH from various gases also has been studied and, with methanol, the yield of CH relative to OH. Astronomical studies of CH in higher rotational levels and (13)CH can now be undertaken on the basis of the present work.

Astronomical Phenomena↗

PubMed2006

Monobridged Si2H4.

The rotational spectrum of a new monobridged isomer of Si(2)H(4), denoted here as H(2)Si(H)SiH, has been detected by Fourier transform microwave spectroscopy of a supersonic molecular beam through the discharge products of silane. On the basis of high-level coupled cluster theory, this isomer is calculated to lie only 7 kcalmol above disilene (H(2)SiSiH(2)), the most stable isomeric arrangement of Si(2)H(4), and to be fairly polar, with a calculated dipole moment of mu = 1.14 D. The rotational spectrum of H(2)Si(H)SiH exhibits closely spaced line doubling, characteristic of a molecule undergoing high-frequency inversion. Transition state calculations indicate that inversion probably occurs in two steps: migration of the bridged hydrogen atom to form silylsilylene, H(3)SiSiH, and then internal rotation of the SiH(3) group, followed by the reverse process. The potential energy surface for this type of inversion is quite shallow, with a barrier height of only 2-3 kcalmol. Searches for the rotational lines of silylsilylene, calculated to be of comparable stability to H(2)Si(H)SiH but about five times less polar (mu = 0.23 D), have also been undertaken, so far without success, even though strong lines of H(2)Si(H)SiH have been detected. The favorable energetics and high polarity of monobridged Si(2)H(4) with respect to either disilene or silylsilylene make it a plausible candidate for radioastronomical detection in sources such as IRC + 10216, where comparably large silicon molecules such as SiS, SiC(3), and SiC(4) have already been discovered.

Journal Article↗

PubMed2005

Rotational spectra of the carbon-chain radicals HC5O, HC6O, and HC7O.

Three new free carbon-chain radicals, HC5O, HC6O, and HC7O, and their deuterated isotopic species have been observed by Fourier transform microwave spectroscopy of a supersonic molecular beam. In contrast to the shorter HCnO radicals, these all have linear heavy-atom backbones and 2Pi electronic ground states. Like the isovalent HCnS radicals, the ground states of the HCnO radicals alternate with odd and even numbers of carbon atoms: those of HC5O and HC7O are 2Pi1/2 and that of HC6O is 2Pi3/2. From frequency measurements between 6 and 26 GHz, the rotational constant B, the centrifugal distortion constant D, and the lambda-type doubling and magnetic hyperfine constants have been determined to high precision for each chain. Predicted properties from coupled-cluster calculations are also reported for chains up to HC9O. The production of HCnO radicals for n even was highly favored when O2 was used as the source of oxygen, but those with n odd were best produced with CO.

Journal Article↗

PubMed2005

Rotational spectroscopy and equilibrium structures of S3 and S4.

The sulfur molecules thiozone S3 and tetrasulfur S4 have been observed in a supersonic molecular beam in the centimeter-wave band by Fourier transform microwave spectroscopy, and in the millimeter- and submillimeter-wave bands in a low-pressure glow discharge. For S3 over 150 rotational transitions between 10 and 458 GHz were measured, and for S4 a comparable number between 6 and 271 GHz. The spectrum of S3 is reproduced to within the measurement uncertainties by an asymmetric top Hamiltonian with three rotational and 12 centrifugal distortion constants; ten distortion constants, but an additional term to account for very small level shifts caused by interchange tunneling, are required to reproduce to comparable accuracy the spectrum of S4. Empirical equilibrium (r(e)(emp)) structures of S3 and S4 were derived from experimental rotational constants of the normal and sulfur-34 species and vibrational corrections from coupled-cluster theory calculations. Quantum chemical calculations show that interchange tunneling occurs because S4 automerizes through a transition state with D2h symmetry which lies about 500 cm(-1) above the two equivalent C2upsilon minima on the potential energy surface.

Journal Article↗

PubMed2005

Fourier transform microwave spectroscopy of vinyldiacetylene, vinyltriacetylene, and vinylcyanodiacetylene.

The rotational spectra of the three carbon chain molecules vinyldiacetylene (hex-1-ene-3,5-diyne, C(6)H(4)), vinyltriacetylene (oct-1-ene-3,5,7-triyne, C8H4), and its cyano analog vinylcyanodiacetylene (1-cyanohex-5-ene-1,3-diyne, C7H3N) have been observed for the first time by Fourier transform microwave spectroscopy of a supersonic molecular beam. The molecules were observed as products of an electrical discharge through selected precursor mixtures: ethylene/diacetylene and vinylacetylene/diacetylene for the pure hydrocarbon molecules and vinylacetylene/cyanoacetylene for vinylcyanodiacetylene. The measurements yield precise sets of rotational constants that compare very well with theoretical constants obtained by quantum chemical calculations at the B3LYP/cc-pVTZ level of theory. Since these three carbon chains are similar in structure and composition to known astronomical molecules and because of their significant polarity, all three are candidates for radio astronomical detection.

Journal Article↗

PubMed2005

Rotational spectrum and carbon-13 hyperfine structure of the C3H, C5H, C6H, and C7H radicals.

By means of Fourier transform microwave spectroscopy of a supersonic molecular beam, we have detected the singly substituted carbon-13 isotopic species of C(5)H, C(6)H, and C(7)H. Hyperfine structure in the rotational transitions of the lowest-energy fine structure component ((2)Pi(12) for C(5)H and C(7)H, and (2)Pi(32) for C(6)H) of each species was measured between 6 and 22 GHz, and precise rotational, centrifugal distortion, Lambda-doubling, and (13)C hyperfine coupling constants were determined. In addition, resolved hyperfine structure in the lowest rotational transition (J = 32-->12) of the three (13)C isotopic species of C(3)H was measured by the same technique. By combining the centimeter-wave measurements here with previous millimeter-wave data, a complete set of (13)C hyperfine coupling constants were derived to high precision for each isotopic species. Experimental structures (r(0)) have been determined for C(5)H and the two longer carbon-chain radicals, and these are found to be in good agreement with the predictions of high-level coupled-cluster calculations. C(3)H, C(5)H, and C(7)H exhibit a clear alternation in the magnitude and sign of the (13)C hyperfine coupling constants along the carbon-chain backbone. Because the electron spin density is nominally zero at the central carbon atom of C(3)H, C(5)H, and C(7)H, and at alternating sets of carbon atoms of C(5)H and C(7)H, owing to spin polarization, almost all of the (13)C coupling constants at these atoms are small in magnitude and negative in sign. Spin-polarization effects are known to be important for the Fermi-contact (b(F)) term, but prior to the work here they have generally been neglected for the hyperfine terms a, c, and d.

Journal Article↗

PubMed2005

Laser spectroscopy of Si3C.

The C 1B1<--X 1A1 band system of the potential interstellar species Si3C has been recorded in a silane/acetylene discharge by resonant two-color two-photon ionization spectroscopy. The origin band is located near 24,925 cm-1 (3.09 eV). Several other features in the spectrum are assigned to progressions in the Si-Si stretching modes as well as to sequence and hot band transitions. The assignment was facilitated by ab initio calculations, which also indicate that this is the strongest electronic transition of Si3C in the visible region of the spectrum. Features in the spectrum are broadened considerably (ca. 10 cm-1), and suggest an excited state lifetime of a few picoseconds. Possible reasons for the short-lived nature of the excited state are discussed.

Journal Article↗

PubMed2004

Tetrasulfur, S4: rotational spectrum, interchange tunneling, and geometrical structure.

The rotational spectrum of S4 has been observed for the first time in an electrical discharge through sulfur vapor. Two techniques have been used: Fourier transform microwave spectroscopy and long-path millimeter-wave absorption spectroscopy. Small, but systematic shifts of the measured transition frequencies of the normal isotopic species indicate that S4 has C2v symmetry but with a low-lying transition state of D2h symmetry, yielding interchange tunneling at 14.1(2) kHz in its ground vibrational state. From the rotational constants of the normal and the single 34S isotopic species, an experimental (r0) structure has been derived: S4 is a singlet planar trapezoid with a terminal bond length of 1.899(7) A, a central bond of 2.173(32) A, and an S-S-S angle of 103.9(8) degrees. Like thiozone (S3), S4 is a candidate for detection in the atmosphere of the Jovian moon Io and in other astronomical sources.

Journal Article↗

PubMed2003

Mono- and dibridged isomers of Si2H3 and Si2H4: the true ground state global minima. Theory and experiment in concert.

Highly correlated ab initio coupled-cluster theories (e.g., CCSD(T), CCSDT) were applied on the ground electronic states of Si(2)H(3) and Si(2)H(4), with substantive basis sets. A total of 10 isomers, which include mono- and dibridged structures, were investigated. Scalar relativistic corrections and zero-point vibrational energy corrections were included to predict reliable energetics. For Si(2)H(3), we predict an unanticipated monobridged H(2)Si-H-Si-like structure (C(s), (2)A'') to be the lowest energy isomer, in constrast to previous studies which concluded that either H(3)Si-Si (C(s), (2)A'') or near-planar H(2)Si-SiH (C(1), (2)A) is the global minimum. Our results confirm that the disilene isomer, H(2)Si-SiH(2), is the lowest energy isomer for Si(2)H(4) and that it has a trans-bent structure (C(2)(h), (1)A(g)). In addition to the much studied silylsilylene, H(3)Si-SiH, we also find that a new monobridged isomer H(2)Si-H-SiH (C(1), (1)A, designated 2c) is a minimum on the potential energy surface and that it has comparable stability; both isomers are predicted to lie about 7 kcal/mol above disilene. By means of Fourier transform microwave spectroscopy of a supersonic molecular beam, the rotational spectrum of this novel Si(2)H(4) isomer has recently been measured in the laboratory, as has that of the planar H(2)Si-SiH radical. Harmonic vibrational frequencies as well as infrared intensities of all 10 isomers were determined at the cc-pVTZ CCSD(T) level.

Journal Article↗

PubMed2003

Rotational spectrum and structure of Si3.

The rotational spectrum of a pure silicon cluster, the Si3 trimer, has been observed for the first time. From the rotational constants of the normal and the 29Si and 30Si isotopic species, a precise geometrical structure has been derived: the trimer is an isosceles triangle with a bond to the apex Si of length 2.177(1) A and an apex angle of 78.10(3) degrees. The substantial inertial defect and fairly large centrifugal distortion suggest that the molecule possesses a shallow bending potential. Si3 is a good candidate for astronomical detection because radio lines of comparably massive silicon molecules (e.g., SiC2, SiC4, and SiS) are readily observed in at least one astronomical source. The rotational spectra of Si6, Si9, and even larger polar silicon clusters may be detectable with the present technique, as well as similar germanium clusters.

Journal Article↗

PubMed2001

Carbon chains and rings in the laboratory and in space.

Seventy-seven reactive organic molecules of astrophysical interest have been identified in a supersonic molecular beam, 73 in the radio band by Fourier-transform microwave spectroscopy, four in the optical by laser cavity ringdown spectroscopy. Most are linear carbon chains, but six consist of carbon chains attached to the compact, highly polar C3 ring, and two are rhomboidal cyclic configurations of SiC3. The laboratory astrophysics of the radio molecules is complete for the time being, in the sense that essentially all the rotational transitions of current interest to radio astronomy (including hyperfine structure when present) can now be calculated to a small fraction of 1 km s(-1) in equivalent radial velocity; six of the radio molecules have already been detected in space on the basis of the present data. The FTM spectrometer employed in this work is far from fundamental limits of sensitivity, so many more molecules can probably be found by refinements of present techniques. The density of reactive molecules in our supersonic beam is generally high by the standards of laser spectroscopy, and many of the radio molecules probably have detectable optical transitions which we are attempting to find, largely motivated by the long-standing problem of the diffuse interstellar bands. Our most interesting result to date is the detection of a fairly strong molecular band at 443 nm in a benzene discharge, in exact coincidence with the strongest and best known interstellar band. Isotopic shifts measured with partially and totally deuterated benzene suggest that the carrier of the laboratory band is a hydrocarbon molecule with the elemental formula CnH5, with n most likely in the range 3-6.

Astronomical Phenomena↗

PubMed2000

The Radio Spectra of SiCCH, SiCN, and SiNC.

Three new silicon-bearing radicals of astrophysical interest, SiCCH and the two nearly isoenergetic isomers SiCN and SiNC, were detected in a laboratory discharge in their X2Pi ground states by Fourier transform microwave and millimeter-wave absorption spectroscopy. Hyperfine structure was observed in the low rotational transitions of the (2)Pi(1/2) ladder, and well-resolved Lambda-doubling was observed in both fine-structure ladders. With the spectroscopic constants derived from the laboratory measurements, the spectra of all three can be calculated to an uncertainty of less than 0.1 km s(-1) in equivalent radial velocity over the entire range of interest to radio astronomers. SiCN, with a dipole moment of 2.9 D, is probably the most promising of the three for astronomical discovery.

Journal Article↗

PubMed2000

Laboratory Detection of a Molecular Band at lambda4429.

A fairly strong molecular absorption band at 4429.27+/-0.04 Å, closely centered on the strongest diffuse interstellar band at 4428.9+/-1.4 Å, has been found in a supersonic molecular beam among the products of a discharge through benzene and other hydrocarbons. This agreement in wavelength to a few parts in 104 strongly suggests a common carrier. The width of the laboratory band is significantly less than that of the diffuse interstellar band, but this difference may be the result of the very low rotational temperature in the supersonic beam-possibly as low as 2 K-relative to that of a weakly polar molecule in the diffuse interstellar gas (100-200 K). Several candidate carriers are discussed. Two of the more promising are the allyl cation C3H+5 and the dimethylene allenyl radical C5H5, both bent carbon chains that may be close enough to linear to reconcile the puzzling appearance of P-, Q-, and R-branches in the laboratory band with the five hydrogen atoms suggested by the observed deuterium isotopic shifts.

Journal Article↗

PubMed2000

Experimental Structures of the Carbon Chains HC(7)N, HC(9)N, and HC(11)N by Isotopic Substitution.

The effective structures (r(0)) of the three linear cyanopolyynes HC(7)N, HC(9)N, and HC(11)N have been determined to high accuracy by isotopic substitution, following detection in a supersonic molecular beam with a Fourier transform microwave spectrometer of all of the singly substituted rare isotopic species. For each chain, the lengths of the individual bonds have been determined to an accuracy of 0.001 Å or 0.1% toward the end of the chain and to 0.01 Å or 1.0% toward the center. The experimental structures are in excellent agreement with recent high-level theoretical calculations, or, in the case of HC(11)N, with extrapolation from HC(9)N. The three polyynes studied here represent the largest reactive carbon chain molecules for which accurate structures have been derived empirically. For HC(7)N and HC(9)N, it has been possible to resolve at high-resolution nitrogen hyperfine structure in the lower rotational transitions and determine eQq for all of the singly substituted isotopic species of HC(7)N and for normal HC(9)N. Copyright 2000 Academic Press.

Journal Article↗

PubMed1999

Microwave Spectra of the Methylpolyynes CH(3)(C&tbond;C)(6)H and CH(3)(C&tbond;C)(7)H.

Two new methylpolyynes, CH(3)(C&tbond;C)(6)H (tridecahexayne) and CH(3)(C&tbond;C)(7)H (pentadecaheptayne), have been detected in a supersonic molecular beam by Fourier transform microwave spectroscopy. A total of 20 transitions of CH(3)(C&tbond;C)(6)H in the K = 0 and 1 rotational ladders and 8 transitions of CH(3)(C&tbond;C)(7)H in the K = 0 ladder were observed between 5 and 11 GHz, allowing for both molecules precise determination of rotational and centrifugal distortion constants. Like other long carbon chains of similar length, the rotational constants of the two new methylpolyynes are well predicted by extrapolation from the shorter members of the sequence; the addition of successive C(2) units evidently little perturbs the structure of the rest of the molecule. Centrifugal distortion is well described by the same semiclassical model that works well for the cyanopolyynes, one which treats a carbon chain as a thin elastic rod with a Young's modulus independent of length. Copyright 1999 Academic Press.

Journal Article↗

PubMed1999

Electronic Ground and Excited State Spectroscopy of C(6)H and C(6)D.

Rotational transitions in the X(2)Pi ground state of C(6)H and C(6)D have been measured by Fourier transform microwave and millimeter-wave absorption spectroscopy. More than 150 rotational lines in the ground (2)Pi(3/2) and (2)Pi(1/2) ladders have been observed, allowing an accurate determination of the rotational, fine structure, lambda-doubling, and hyperfine coupling constants using a standard effective Hamiltonian for a molecule in an isolated (2)Pi electronic state. The molecular ground state constants are used to characterize the rotationally resolved origin band of the (2)Pi <-- X(2)Pi electronic transition observed by cavity ring-down laser absorption spectroscopy in a pulsed supersonic slit-jet discharge source. From these data, spectroscopic constants for the excited electronic state are determined. Copyright 1999 Academic Press.

Journal Article↗

PubMed1998

Microwave Spectra of the Methylcyanopolyynes CH3(C&tbond;C)nCN, n = 2, 3, 4, 5.

The ground state rotational spectra of four methylcyanopolyynes CH3(C&tbond;C)2CN, CH3(C&tbond;C)3CN, CH3(C&tbond;C)4CN, and CH3(C&tbond;C)5CN were measured between 6 and 22 GHz by Fourier transform microwave spectroscopy. For CH3(C&tbond;C)2CN, previously observed by Alexander et al. [J. Mol. Spectrosc. 70, 84-94 (1978)] eight transitions were observed, each with sufficient resolution to determine the nitrogen quadrupole hyperfine constant for the first time: eqQ = -4.25(3) MHz. The longer three methylcyanopolyynes are new; for these, from 10 to 21 rotational transitions were detected and precise values for the rotational and the leading centrifugal distortion constants, and eqQ for CH3(C&tbond;C)3CN, were determined. Copyright 1998 Academic Press.

Journal Article↗