Spin-rotation Coupling Constants Research Articles

Simulation and analysis of 13C spin-rotation nuclear magnetic resonance relaxation rates of methyl groups

This work analyzes the nuclear spin–rotation contribution to the nuclear magnetic resonance relaxation of methyl groups from 10 rigid compounds (eight benzene derivatives with one, two, or three methyl groups and two bicyclic molecules) with internal rotation axes not aligned to the smallest molecular moment of inertia via molecular dynamics simulation and ab initio calculation. The molecular dynamics simulation and ab initio calculation of nuclear spin-rotation coupling constants reproduce the experimental behavior in selected systems. The presented methodology can help in the analysis and interpretation of experimental relaxation data.

The electronic system and of LiCa

High-resolution Fourier transform spectroscopy and Laser-induced fluorescence have been performed on LiCa in the infrared spectral range. We analyse rovibrational transitions of the – system of LiCa and find the state to be perturbed by spin–orbit coupling to the state. We study the coupled system obtaining molecular parameters for the and the state together with effective spin–orbit and spin–rotation coupling constants. The coupled system has also been evaluated by applying a potential function instead of rovibrational molecular parameters for the state . An improved analytic potential function of the state is derived, due to the extension of the observed rotational ladder.

Microwave spectrum and iodine nuclear quadrupole coupling constants of 1,1-diiodoethane

The high resolution rotational spectroscopic observation of 1,1-diiodoethane is investigated using a pulsed jet, cavity Fourier transform microwave (FTMW) spectrometer over the frequency range 11.5–18 GHz for the first time. The rotational constants, the centrifugal distortion constants, the nuclear spin-rotation coupling constants, and the complete tensor components of the nuclear quadrupole coupling for both iodine nuclei have been determined and reported. The fitted rotational constants are A = 4548.320446(47), B = 625.629141(55), C = 558.798939(43) MHz and the nuclear quadrupole coupling constants are χaa = −1089.8125(7), χbb − χcc = −542.3162(13), |χab| = 1215.7505(10), χbc = 340.8983(14), and |χac| = 562.4206(19) MHz. No A-E splittings due to the methyl group internal rotation were observed. Many dipole-forbidden/electric quadrupole coupling allowed transitions were observed in the spectrum due to the large iodine quadrupole coupling effect. Quantum chemical calculations were performed at the CCSD(T)/aug-cc-pVTZ-pp level of theory. The calculated rotational constants, centrifugal distortion constants, and hyperfine constants were used to guide the data analysis.

Positions and intensities of hyperfine components of all rovibrational dipole lines in the HD molecule

We report results of a theoretical analysis of hyperfine interactions in the HD molecule. We present the calculated coupling constants: spin-rotation, spin-spin and electric quadrupole coupling constants for all bound states of HD in its ground electronic 1Σ state. We provide a list of positions and intensities of 108 320 hyperfine components of 5 129 dipole transitions from the P and R branches. The positions and intensities of the hyperfine components are necessary for a proper interpretation of accurate measurements of rovibrational transition frequencies in HD which are used for tests of quantum electrodynamics of molecules and searches for new physics beyond the Standard Model.

Broadband Microwave Spectroscopy of 2-Furanyloxy Radical: Primary Pyrolysis Product of the Second-Generation Biofuel 2-Methoxyfuran.

Broadband microwave spectra over the 2-18 GHz range have been recorded for the resonance-stabilized 2-furanyloxy radical, formed in the first step of pyrolysis of the second-generation biofuel 2-methoxyfuran by methyl loss. Using a flash pyrolysis source attached to a pulsed valve, a 0.7% mixture of 2-methoxyfuran in argon was pyrolyzed at a series of temperatures ranging from 300 to 1600 K. Subsequent cooling in a supersonic expansion produced rotational temperatures of ∼2 K in the interrogation region. Using chirped-pulse Fourier transform microwave (CP-FTMW) methods, combined with strong-field coherence breaking (SFCB), a set of transitions due to the radical were identified and assigned. The experimental rotational constants ( A = 8897.732(93), B = 4019.946(24), C = 2770.321(84)), centrifugal distortion constants, and spin-rotation coupling constants have been determined for the radical and compared with ab initio predictions at the CCSD(T) level of theory. Compared to the 2-methoxyfuran precursor, the 2-furanyloxy radical has allylic C-C bond lengths intermediate between single and double bonds, a shortened C(5)-O(6) bond characteristic of partial double-bond character, and an O(1)-C(5)-O(6) bond angle of 121°, which resembles the O-C-O angle of an ester. Atomic spin densities extracted from the calculations confirm that the 2-furanyloxy radical is best viewed as a carbon-centered allylic lactone radical, with 80% of the spin density on the two allylic carbons and 20% on the pendant O(6) atom.

Big picture of relativistic molecular quantum mechanics

Abstract Any quantum mechanical calculation on electronic structure ought to choose first an appropriate Hamiltonian H and then an Ansatz for parameterizing the wave function Ψ, from which the desired energy/property E(λ) can finally be calculated. Therefore, the very first question is: what is the most accurate many-electron Hamiltonian H? It is shown that such a Hamiltonian i.e. effective quantum electrodynamics (eQED) Hamiltonian, can be obtained naturally by incorporating properly the charge conjugation symmetry when normal ordering the second quantized fermion operators. Taking this eQED Hamiltonian as the basis, various approximate relativistic many-electron Hamiltonians can be obtained based entirely on physical arguments. All these Hamiltonians together form a complete and continuous ‘Hamiltonian ladder’, from which one can pick up the right one according to the target physics and accuracy. As for the many-electron wave function Ψ, the most intriguing questions are as follows. (i) How to do relativistic explicit correlation? (ii) How to handle strong correlation? Both general principles and practical strategies are outlined here to handle these issues. Among the electronic properties E(λ) that sample the electronic wave function nearby the nuclear region, nuclear magnetic resonance (NMR) shielding and nuclear spin-rotation (NSR) coupling constant are especially challenging: they require body-fixed molecular Hamiltonians that treat both the electrons and nuclei as relativistic quantum particles. Nevertheless, they have been formulated rigorously. In particular, a very robust ‘relativistic mapping’ between the two properties has been established, which can translate experimentally measured NSR coupling constants to very accurate absolute NMR shielding scales that otherwise cannot be obtained experimentally. Since the most general and fundamental issues pertinent to all the three components of the quantum mechanical equation HΨ = EΨ (i.e. Hamiltonian H, wave function Ψ, and energy/property E(λ)) have fully been understood, the big picture of relativistic molecular quantum mechanics can now be regarded as established.

Terahertz spectroscopy of methanimine and its isotopologs

Context. Methanimine (CH2NH) is a simple molecule composed of methylene and imine. The molecule has been detected toward the Galactic center, star-forming regions, circumstellar envelopes, and other galaxies since 1973. In previous studies, the rest frequency of methanimine has been measured for normal species up to the 650-GHz region, but its 13 CH2NH, CH2 15 NH, and CH2ND isotopologs were limited to the 100-GHz region. Aims. If a rotational temperature of 100 K is assumed for methanimine, the highest intensity falls at approximately 1.5 THz. In addition to normal methanimine, the 13 CH2NH, CH2 15 NH, and CH2ND isotopologs in their ground-vibrational states were observed in the frequency range of 120–1600 GHz to provide accurate rest frequency information. Based on this study, the calculated rest frequencies below 2 THz should be sufficiently precise and support observations using all ALMA and Herschel/HIFI observational bands. Methods. Methanimine was generated by pyrolysis of diaminoethane (DAE) vapor at 850 ◦ C. 13 CH2NH and CH2 15 NH isotopologs were measured with their natural abundance, and deuterization of DAE was performed by mixing normal DAE with deuterated water, D2O, and then pyrolyzed. This gives the deuterated isotopolog of methanimine, CH2ND. Spectral measurements were performed by using the 23 kHz source-frequency modulated terahertz spectrometer at Toho University. Results. Both a -a ndb-type transitions up to 1.6 THz for the three isotopologs and the normal species were measured. Rotational and centrifugal distortion constants for the three isotopologs were accurately determined. For normal species (CH2NH), both electric quadrupole and nuclear spin-rotation coupling constants for nitrogen nucleus were determined, while for the 13 CH2NH and CH2ND species, only electric quadrupole-coupling constants for nitrogen nucleus were determined. Conclusions. Our spectral line frequencies are suitable for a future astronomical search for these isotopologs of methanimine. The 1σ frequency accuracy up to 2 THz is lower than 100 kHz.

Fourier-transform microwave spectroscopy of the H2–H2O complex

Fourier-transform microwave spectroscopy was applied to observe the J=1–0 rotational transition of the ortho-H2–H2O complex and isotopologues in the ground Σ0 state (H2 in the jH2=1 state and H2O in the ground 000 state) to obtain precise molecular constants. Observed spectra were split into three hyperfine components, confirming the complexes are the ortho-H2/para-D2 species. The determined nuclear spin–spin coupling constant indicates H2 is rotating almost freely in the complex; the Σ0 state is nearly of jH2=1 and kH2=0. For the ortho-H2 species, the nuclear spin–rotation coupling constant was also determined.

Rotationally resolved ${\tilde{B}} \leftarrow {\tilde{X}}$B̃←X̃ electronic spectra of the isopropoxy radical: A comparative study

The B̃-X̃ laser-induced-fluorescence spectrum of jet-cooled isopropoxy radical (i-C3H7O[middle dot]) has been recorded. Using an isolated state model the observed rotational and fine structure of the origin band has been well simulated to determine rotational constants for both the X̃ and B̃ states and the electron spin-rotation constants of the X̃ state. The line intensities are well simulated with a parallel transition type, requiring the same symmetry for the levels involved of each the X̃ and B̃ state, which confirms the previous suggestion that going from ethoxy (C2H5O[middle dot]) to isopropoxy, the energy ordering of the electron configurations with in- and out-of-plane half-filled p-orbitals of the oxygen atom is reversed and the ground vibronic symmetry changes from a" to a'. However, the observed spin-rotation coupling constants are not consistent with their predication from either semi-empirical theory or quantum chemical calculations. Additionally, the lack of observed transitions involving the out-of-plane transition moment component is not consistent with high level electronic structure calculations suggesting mixing of vibronic levels by strong spin-orbit coupling. A new twofold model has been developed that explicitly includes Coriolis and spin-orbit coupling between different vibronic levels. This model renders the discrepancy between theoretical and experimental spin-rotation constants moot. Moreover, it determines independently the contributions to the observed splitting between the lowest two levels, resulting from non-relativistic kinetic and Coulombic effects, and that due to the relativistic spin-orbit interaction. The experimental values show that these effects are comparable, but that the vibronic one is slightly more important. This result is at variance with state-of-the-art electronic structure calculations which otherwise do a remarkably good job of describing the ground state of isopropoxy.

Electronic spectroscopy of the [formula omitted] transition of DCO and lifetimes and relative quantum yields of the [formula omitted] state

We have measured the laser induced fluorescence excitation spectrum of the origin of the DCO B ∼ ( 2 A ′ ) ← X ∼ ( 2 A ′ ) transition under a variety of experimental conditions, ranging from cooled to 7 K in a supersonic jet, to nascent in the photolysis of D 2CO. By analysing successively more complex spectra we have derived rotational, centrifugal distortion, and spin-rotation coupling constants that provided the best fit to the experimental frequencies. Fluorescence lifetimes were measured for 35 rotationally-resolved excited states, which provided relative quantum yields for these states. Unlike HCO, the lifetimes showed only a weak dependence on N and K a , evincing a weaker coupling between the A ∼ and B ∼ states in DCO than HCO. Intensity ratios for pairs of transitions with the same lower state were used to extract the transition moment angle, θ = 44.6 ± 2.5° and the axis switching angle, ϕ = 3.1 ± 0.5° for the B ∼ – X ∼ transition. Both angles are consistent with the expected change upon deuteration of HCO.

The Zeeman effect and hyperfine interactions in J = 1–0 transitions of CH+ and its isotopologues

The J = 1-0 transitions of (12)CH(+), (13)CH(+), and (12)CD(+) in the ground X(1)Σ(+) state have been unambiguously identified by using an extended negative glow discharge as an ion source. Unexpectedly large Zeeman splittings have been observed, and the (13)CH(+) line exhibits nuclear spin-rotation hyperfine splitting in addition to the Zeeman effect. The nuclear spin-rotation coupling constant was determined to be 1.087(50) MHz for the (13)C species. The rotational g-factor is found to be -7.65(29), in terms of the nuclear magneton for the J = 1 and v = 0 state, more than an order of magnitude larger than values for typical diamagnetic closed shell molecules. These larger than usual magnetic interactions for a (1)Σ molecule are caused by the large rotational energy and relatively small excitation energy of the excited A(1)Π state. The effective g-factor and the spin-rotation coupling constant obtained by ab initio calculations agree very well with the experimentally determined values.

Determination of nuclear spin–rotation coupling constants in CF 3I by chirped-pulse Fourier-transform microwave spectroscopy

The rotational spectrum of CF 3I in the ground vibrational state has been re-measured using a chirped-pulse Fourier-transform microwave spectrometer recently constructed at the University of Bristol. The new spectrometer provides the capability to acquire broadband rotational spectra throughout an operational frequency range of 7–18 GHz. The frequencies of ninety-nine F 1′– F 1″ transitions in three distinct J K ′– J K ″ bands have been recorded during an experiment which required only a couple of hours of data collection. Many of these transitions have additionally been re-measured using a Balle–Flygare, Fourier-transform microwave spectrometer. Fitting the data to the Hamiltonian for a C 3v prolate, symmetric top has allowed the determination of new spectroscopic parameters. The rotational constant, B 0, and nuclear quadrupole coupling constant, χ aa ( I ) , are consistent with the results provided in earlier works. The nuclear magnetic spin–rotation constants, C perp.(I) and C perp.(F), have been independently determined for the first time. These parameters are evaluated as 6.92(5) kHz and 2.37(11) kHz respectively. A technical description of the new CP-FTMW instrument is presented.

Fourier transform microwave spectroscopy of HZnCN(X Σ1+) and ZnCN(X Σ2+)

The pure rotational spectrum of HZnCN in its X (1)Sigma(+) electronic state has been recorded using pulsed Fourier transform microwave (FTMW) techniques in the frequency range 7-39 GHz-the first spectroscopic study of this species in the gas phase. The FTMW spectrum of ZnCN(X (2)Sigma(+)) has been measured as well. A new FTMW spectrometer with an angled beam and simplified electronics, based on a cryopump, was employed for these experiments. The molecules were created in a dc discharge from a gas mixture of Zn(CH(3))(2) and cyanogen (1% D(2) for the deuterated analogs), diluted with argon, that was expanded supersonically from a pulsed nozzle. Seven isotopologues of HZnCN arising from zinc, deuterium, and (13)C substitutions were studied; for every species, between three and five rotational transitions were recorded, each consisting of numerous hyperfine components arising from nitrogen, and in certain cases, deuterium, and 67-zinc nuclear spins. Four transitions of ZnCN were measured. From these data, rotational, nuclear spin-rotation, and quadrupole coupling constants have been determined for HZnCN, as well as rotational, and magnetic and quadrupole hyperfine parameters for the ZnCN radical. The bond lengths determined for HZnCN are r(H-Zn)=1.495 A, r(Zn-C)=1.897 A, and r(C-N)=1.146 A, while those for ZnCN are r(Zn-C)=1.950 A and r(C-N)=1.142 A. The zinc-carbon bond length thus shortens with the addition of the H atom. The nitrogen quadrupole coupling constant eqQ was found to be virtually identical in both cyanide species (-5.089 and -4.931 MHz), suggesting that the electric field gradient across the N nucleus is not influenced by the H atom. The quadrupole constant for the (67)Zn nucleus in H(67)ZnCN is unusually large relative to that in (67)ZnF (-104.578 versus -60 MHz), evidence that the bonding in the cyanide has more covalent character than in the fluoride. This study additionally suggests that hydrides of other metal cyanide species are likely candidates for high resolution spectroscopic investigations.

An investigation of the molecular geometry and electronic structure of nitryl chloride by a combination of rotational spectroscopy and ab initio calculations

The ground-state rotational spectra of the six isotopomers (16)O(2) (14)N(35)Cl, (16)O(2) (14)N(37)Cl, (18)O(16)O(14)N(35)Cl, (18)O(2) (14)N(35)Cl, (16)O(2) (15)N(35)Cl, and (16)O(2) (15)N(37)Cl of nitryl chloride were observed with a pulsed-jet, Fourier-transform microwave spectrometer to give rotational constants, Cl and (14)N nuclear quadrupole coupling, and spin-rotation coupling constants. These spectroscopic constants were interpreted to give r(0), r(s), and r(m) ((2)) versions of the molecular geometry and information about the electronic redistribution at N when nitryl chloride is formed from NO(2) and a Cl atom. The r(m) ((2)) geometry has r(N-Cl)=1.8405(6) A, r(N-O)=1.1929(2) A, and the angle ONO=131.42(4) degrees , while the corresponding quantities for the r(s) geometry are 1.8489 A, 1.1940 A, and 131.73 degrees , respectively. Electronic structure calculations at CCSD(T)cc-pVXZ (X=T, Q, or 5) levels of theory were carried out to give a r(e) geometry, vibration-rotation corrections to equilibrium rotational constants, and values of the (35)Cl and (14)N nuclear hyperfine (quadrupole and spin-rotation) coupling constants in good agreement with experiment. The equilibrium geometry at the CCSD(T)/cc-pV5Z level of theory has r(N-Cl)=1.8441 A, r(N-O)=1.1925 A and the angle ONO=131.80 degrees . The observed rotational constants were corrected for the vibration-rotation effects calculated ab initio to yield semiempirical equilibrium constants which were then fitted to give the following semiempirical equilibrium geometry: r(N-Cl)=1.8467(2) A, r(N-O)=1.1916(1) A, and the angle ONO=131.78(3) degrees .

Rotational spectra, potential function, Born–Oppenheimer breakdown and magnetic shielding of SiSe and SiTe

The pure rotational spectra of 18 isotopic species of SiSe (8) and SiTe (10) have been measured in their X 1Σ + electronic state with a pulsed-jet resonator Fourier transform microwave spectrometer. The molecules were prepared by a combined DC discharge/laser ablation technique and stabilised in a supersonic jet of Ar. Global multi-isotopologue analyses yielded spectroscopic Dunham parameters Y 01, Y 11, Y 21, Y 31 and Y 02 for both species, as well as effective Born–Oppenheimer breakdown (BOB) coefficients δ 01 for Si, Se and Te. A direct fit of the same data sets to an appropriate radial Hamiltonian yielded analytic potential energy functions and BOB radial functions for the X 1Σ + electronic state of both SiSe and SiTe. Additionally, the magnetic hyperfine interactions produced by the uneven mass number A nuclei 29Si, 77Se and 125Te were observed, yielding first determinations of the corresponding nuclear spin–rotation coupling constants.

Sub-Doppler millimetre-wave spectroscopy of DBS and HBS: accurate values of nuclear electric and magnetic hyperfine structure constants

The unstable thioborine molecule and its deuterated variant have been produced by a high-temperature reaction between hydrogen sulfide and crystalline boron at 1100 degrees C in a flow system. Five rotational transitions from J = 2 <-- 1, to J = 6 <-- 5 have been recorded with sub-Doppler resolution for the vibrational ground state of H10/11BS and D10/11BS using the Lamb-dip technique. The hyperfine structure due to the electric quadrupole interaction of deuterium nucleus has been resolved yielding the first experimental determination of the deuterium quadrupole coupling constant in thioborine, which is 0.1403(75) MHz in D11 BS and 0.1360(38) MHz in D10BS. Fairly accurate values of 10/11B spin-rotation coupling constants and of the hydrogen-boron spin-spin coupling constants have also been determined. Additionally, the hyperfine structure of the rotational lines for the nu2 = 1 excited state has been investigated, thus obtaining information on the asymmetry of the electric field gradient at the B nucleus in the bending state.

Pure rotational spectra of PbSe and PbTe: potential function, Born–Oppenheimer breakdown, field shift effect and magnetic shielding

The pure rotational spectra of 41 isotopic species of PbSe and PbTe have been measured in their X 1Sigma+ electronic state with a resonator pulsed-jet Fourier transform microwave spectrometer. The molecules were prepared by laser ablation of suitable target rods and stabilised in supersonic jets of noble gas. Global multi-isotopologue analyses yielded spectroscopic Dunham parameters Y01, Y11, Y21, Y31, Y02, and Y12 for both species, as well as effective Born-Oppenheimer breakdown (BOB) coefficients delta01 for Pb, Se and Te. Unusual large values of the BOB parameters for Pb have been rationalized in terms of finite nuclear size (field shift) effect. A direct fit of the same data sets to an appropriate radial Hamiltonian yielded analytic potential energy functions and BOB radial functions for the X 1Sigma+ electronic state of both PbSe and PbTe. Additionally, the magnetic hyperfine interactions produced by the uneven mass number A nuclei 207Pb, 77Se, 123Te, and 125Te were observed, yielding first determinations of the corresponding nuclear spin-rotation coupling constants.

The rotational spectra, potential function, Born-Oppenheimer breakdown, and magnetic shielding of SnSe and SnTe

The pure rotational spectra of 27 isotopic species of SnSe and SnTe have been measured in the frequency range of 5-24 GHz using a Fabry-Perot-type resonator pulsed-jet Fourier-transform microwave spectrometer. Gaseous samples of both chalcogenides were prepared by laser ablation of suitable target rods and were stabilized in supersonic jets of Ar. Global multi-isotopolog analyses of all available high-resolution data produced spectroscopic Dunham parameters Y01, Y11, Y21, Y31, Y02, and Y12 for both species, as well as Born-Oppenheimer breakdown (BOB) coefficients delta01 for Sn, Se, and Te. A direct fit of the same data sets to an appropriate radial Hamiltonian yielded analytic potential energy functions and BOB radial functions for the X 1Sigma+ electronic state of both SnSe and SnTe. Additionally, the magnetic hyperfine interaction produced by the dipolar nuclei 119Sn, 117Sn, 77Se, and 125Te was observed, yielding first determinations of the corresponding spin-rotation coupling constants.

The pure rotational spectrum of TeSe: Rotational parameters, Born–Oppenheimer breakdown corrections, and hyperfine constants

The characterization of tellurium selenide in its electronic ground state (X0 + ∑ − ) was possible by using LASER-ablation to isolate the diatomic in a pulsed molecular beam and by applying Fourier transform microwave spectroscopy to obtain the pure rotational spectrum. Employing a global multi-isotopologue analysis to transitions of 43 isotopologues of TeSe in seven vibrational states spectroscopic Dunham parameters Y ℓ , m , Born–Oppenheimer breakdown coefficients δ ℓ , m , the equilibrium bond lengths r e, as well as the vibration parameters ω e and ω e x e were obtained for all analysed isotopologues. For low vibrational states, the Morse-potential function describes the TeSe-potential very well and provides an estimate of the maximum dissociation energy for this semi-metal compound. In addition, the isotopologue independent molecular constants U ℓ , m and the corresponding Born–Oppenheimer breakdown coefficients Δ ℓ , m were determined. Quite large coefficients Δ 0 , 1 Te and Δ 0 , 1 Se were necessary for Watson's reference isotopologue independent analysis. This is rationalized by the interaction between the two sublevels of the electronic 3Σ-state. Also the magnetic spin–rotation coupling constants that were achieved for some of the isotopologues reflect this electronic ground state. Field shift effects are found to be negligible.

OC [sbnd]Cu [sbnd]I synthesized by reaction of laser-ablated Cu with a CH 3I/CO/Ar mixture and characterised by pulsed-jet, Fourier-transform microwave spectroscopy

OC Cu I, previously uncharacterised in the gas phase, was generated by the reaction of laser-ablated Cu with methyl iodide contained in a mixture of argon and CO. The Cu I initially formed picks up CO to yield OC Cu I. The rotational spectrum was observed by means of a pulsed-jet, Fourier-transform microwave spectrometer. The rotational constants B 0, centrifugal distortion constants D 0, nuclear quadrupole coupling constants and spin-rotation coupling constants for Cu and I were determined for the four isotopomers 16O 12C 63Cu 127I, 16O 12C 65Cu 127I, 18O 12C 63Cu 127I and 16O 13C 63Cu 127I. Geometries of the r 0, r s and r m type are presented and changes in the electronic structure when OC Cu I is formed from Cu I are discussed.