Triplet-triplet absorption spectra of quinoline and isoquinoline

The difference between the singlet-singlet and the triplet-triplet absorption spectra of quinoline and isoquinoline has been measured from 45 000 to 15 000 cm^?1, in a rigid hydrocarbon glass at 77 K, using a newly constructed computer controlled spectrograph. Both molecules show strong new triplet-triplet absorption bands in the ultraviolet region. Similar bands have recently been found in naphthalene and were assigned to transitions from the lowest triplet state to a triplet state which is doubly excited with respect to the closed shell ground state.     

CP-violation and electric dipole moments

Searches for intrinsic electric dipole moments of nucleons, atoms and molecules are precision flavour-diagonal probes of new -odd physics. We review and summarise the effective field theory analysis of the observable EDMs in terms of a general set of CP-odd operators at 1 GeV, and the ensuing model-independent constraints on new physics. We also discuss the implications for supersymmetric models, in light of the mass limits emerging from the LHC.     

New measurements and global analysis of rotational spectra of Cl-, Br-, and I-benzene: Spectroscopic constants and electric dipole moments

The data available from rotational spectroscopy for chlorobenzene, bromobenzene, and iodobenzene have been extended by new measurements in the mm-wave region and in supersonic expansion in the cm-wave region. All available ground state measurements have been combined in global fits to derive precise rotational, centrifugal, and nuclear quadrupole coupling constants for the molecules. Rotational transitions in first excited states of the lowest frequency normal modes in bromobenzene and iodobenzene have been assigned and fitted. The values of electric dipole moments for ³⁵Cl-, ⁷⁹Br-, ⁸¹Br-, and I-benzene have been determined from Stark effect measurements on selected hyperfine components in the supersonic expansion spectrum, and are compared with values for several other series of monohalogen molecules.     

Relationship between proton shielding constants and electric dipole moments in the hydrogen halides

The proton shielding constants of the hydrogen halides have been calculated employing a molecular wave function built from gauge-invariant atomic orbitals. Each of the molecular wave functions contains a single parameter which is determined from the observed dipole moment. Calculated and experimental values of the shielding constants for HF, HCl, HBr and HI agree to within approximately 10 per cent.     

Microwave spectra,nuclear quadrupole coupling constants,dipole moments,and rotational isomers of propargylimine

The microwave spectra of the short-lived molecule, propargylimine (CHCCHNH), produced by the pyrolysis of dipropargylamine, have been observed. The spectra are analyzed with the aid of an ab initio MO calculation, and the rotational constants for the two isomers (Z- and E-propargylimines) have been determined as A = 54640.228 MHz, B = 4862.4191 MHz, and C = 4458.1986 MHz, and A = 63099.320 MHz, B = 4766.6104 MHz, and C = 4425.5144 MHz, respectively. The dipole moments, the quadrupole coupling constants, and the relative populations between the two isomers have also been obtained.     

Rotational spectra, conformational structures, and dipole moments of thiodiglycol by jet-cooled FTMW and ab initio calculations

The rotational spectra of three low-energy conformers of thiodiglycol (TDG) (HOCH₂CH₂SCH₂CH₂OH) have been measured in a molecular beam using a pulsed-nozzle Fourier-transform microwave spectrometer. To determine the likely conformational structures with ab initio approach, conformational structures of 2-(ethylthio)ethanol (HOEES) (CH₃CH₂SCH₂CH₂OH) were used as starting points together with the consideration of possible intramolecular hydrogen bonding in TDG. Three lower-energy conformers have been found for TDG at the MP2=Full/6311G** level and ab initio results agree nicely with experimentally determined rotational constants. In addition, Stark measurements were performed for two of the three conformers for dipole moment determinations, adding to our confidence of the conformational structure matches between experimental observations and ab initio calculations. Of the three lower-energy conformers, one displays a compact folded-like structure with strong hydrogen bonding between the two hydroxyl groups and the central sulfide atom. Two other conformers have relatively open chain-like structures with hydrogen bonding between each of the hydroxyl groups to the central sulfur atom, of which one has pure b-type dipole moment according to the ab initio results.     

Additional stringy sources for electric dipole moments

We show that string models with low energy supersymmetry which accommodate the fermion mass hierarchy generally give nonuniversal soft trilinear couplings (A terms). In conjunction with the apparently large Cabibbo-Kobayashi-Maskawa (CKM) phase, this results in large fermion electric dipole moments (EDMs) even in the absence of CP violating phases in the supersymmetry breaking auxiliary fields and the micro term. Nonobservation of the EDMs therefore implies that strings select special flavor and/or supersymmetry breaking patterns.     

Intrinsic electric dipole moments of paramagnetic atoms: rubidium and cesium

The electric dipole moment (EDM) of paramagnetic atoms is sensitive to the intrinsic EDM contribution from that of its constituent electrons and a scalar-pseudoscalar (S-PS) electron-nucleus interaction. The electron EDM and the S-PS contributions to the EDMs of these atoms scale as approximately Z;{3}. Thus, the heavy paramagnetic atoms will exhibit large EDM enhancement factors. However, the sizes of the couplings are so small that they are of interest of high precision atomic experiments. In this work we have computed the EDM enhancement factors of the ground states of Rb and Cs due to both the electron EDM and the S-PS EDM using the relativistic coupled-cluster theory. The importance of determining precise ab initio enhancement factors and experimental results of atomic EDMs in deducing a reliable limit on the electron EDM is emphasized.     

The microwave spectra and dipole moments of the cyanopyridines

Rotational transitions of 4-cyanopyridine, 3-cyanopyridine and 2-cyanopyridine have been observed and assigned. The values of the rotational constants for these three molecules are (in MHz):

$\text{4-cyanopyridine}\text{A=6000.}\text{B=1541.19}\text{C=1226.00}\text{3-cyanopyridine}\text{A=5823.01}\text{B=1571.34}\text{=1237.17}\text{2-cyanopyridine}\text{A=5835.756}\text{1598.219}\text{1254.460}$

The dipole moment components were also measured and are (in Debye):

$\text{4-cyanopyridine}\text{μ}{}_{\mathrm{a}}\text{=1.96}\text{μ}{}_{\mathrm{b}}\text{=0}\text{μ}{}_{\mathrm{total}}\text{=1.96}\text{3-cyanopyridine}\text{μ}{}_{\mathrm{a}}\text{=3.13}\text{μ}{}_{\mathrm{b}}\text{=1.90}\text{μ}{}_{\mathrm{total}}\text{=3.66}\text{2-cyanopyridine}\text{μ}{}_{\mathrm{a}}\text{=5.47}\text{μ}{}_{\mathrm{b}}\text{=1.87}\text{μ}{}_{\mathrm{total}}\text{=5.78}$

     

The relative electric dipole moments of singlets and triplets

A sensitivity analysis formalism is constructed for collinear reactive systems with multiple electronic potential energy surfaces. The work extends the sphere of application of sensitivity theory into the reactive domain. Expressions are obtained for the first order elementary sensitivity coefficients (i.e. partial derivatives) of both the reactive and non-reactive component elements of the scattering matrix with respect to an arbitrary system parameter. In the case of the non-reactive elements, the sensitivity coefficients involve essentially the piecewise integration of a function matrix containing the available solution of the scattering problem. The reactive sensitivity coefficients draw on both forward and backward propagated solutions. The paper concludes with a discussion of the scope and applicability of reactive sensitivity analysis.     

Relation between electric quadrupole and magnetic dipole nuclear moments

The values of electric quadrupole moments are described by gyromagnetic ratios of bound and free nucleons. A comparison with the experimental data shows an agreement within 15% for non-magic strongly deformed nuclei and within 50% for other ones. The expressions obtained are sensitive to a change in the order of subshell filling which takes place for proton and neutron subshells near Fermi surface.     

Search for electric dipole moments at storage rings

Twenty years ago, we published a paper entitled “Discovery of antiproton trapping by long-lived metastable states in liquid helium”. In retrospect, this was the discovery of antiprotonic helium atoms, the study of which is actively being done at CERN’s antiproton decelerator. A brief overview of this interesting exotic atom is given, together with some historical background.     

Nuclear electric dipole moments at ion storage rings

Upper limits on the electric dipole moments (EDM) of elementary particles and atoms are presented, and their physical implications are discussed. The implications following from the neutron and atomic experiments are of comparable interest. The nuclear EDMs can be studied at ion storage rings, with the expected sensitivity much better than . This would represent a serious progress in studies of the CP-violation problem. This revised version was published online in August 2006 with corrections to the Cover Date.     

Bino-driven electroweak baryogenesis with highly suppressed electric dipole moments

It is conventional wisdom that successful electroweak baryogenesis in the Minimal Supersymmetric extension of the Standard Model (MSSM) is in tension with the non-observation of electric dipole moments (EDMs), since the level of CP-violation responsible for electroweak baryogenesis is believed to generate unavoidably large EDMs. We show that CP-violation in the bino–Higgsino sector of the MSSM can account for successful electroweak baryogenesis without inducing large EDMs. This observation weakens the correlation between electroweak baryogenesis and EDMs, and makes the bino-driven electroweak baryogenesis scenario the least constrained by EDM limits. Taking this observation together with the requirement of a strongly first-order electroweak phase transition, we argue that a bino-driven scenario with a light stop is the most phenomenologically viable MSSM electroweak baryogenesis scenario.     

Flavour-dependent CP violation and natural suppression of the electric dipole moments

We revisit the supersymmetric CP problem and find that it can be naturally resolved if the origin of CP violation is closely related to the origin of flavour structures. In this case, the supersymmetry breaking dynamics do not bring in any new CP-violating phases. This mechanism requires hermitian Yukawa matrices which naturally arise in models with a U(3) flavour symmetry. The neutron electric dipole moment (NEDM) is predicted to be within one-two orders of magnitude below the current experimental limit. The model also predicts a strong correlation between A_CP(b→sγ) and the NEDM. The strong CP problem is mitigated although not completely solved.     

New method of measuring electric dipole moments in storage rings

A new highly sensitive method of looking for electric dipole moments of charged particles in storage rings is described. The major systematic errors inherent in the method are addressed and ways to minimize them are suggested. It seems possible to measure the muon EDM to levels that test speculative theories beyond the standard model.     

Rotational spectra, conformational structures and dipole moments of 2-(ethylthio)ethanol by jet-cooled FTMW and ab initio calculations

The rotational spectra of three low-energy conformers of 2-(ethylthio)ethanol also known as ethyl 2-hydroxyethylsulfide or hydroxyethyl ethyl sulfide (HOEES), together with the monosubstituted ¹³C and ³⁴S isotopic forms of the two lowest energy conformers, have been measured in a molecular beam using a pulsed-nozzle Fourier-transform microwave spectrometer. To search for the likely conformational structures, ab initio calculations were performed at the MP2/6-31G* level for reduced dimensionality potential energy mapping and at the MP2=FULL/6-311G** and B3LYP=FULL/6-311G** levels for full structural optimization and electronic energy calculations of possible lower energy conformers. In all, five low-energy conformers, each of C₁ point group symmetry, were located in the ab initio search with complete information obtained on rotational constants, dipole moments, and structures. Rotational constants for three of the conformers agree well with the experimental observations, leaving the other two with no experimental partners. The three having experimental matches display relatively open “chain-like” structures corresponding to TG-, and GG-like forms, while the two with no experimental matches display relatively closed or “folded” structures with significantly different rotational constants. Although results using different ab initio level theories with and without zero point energy corrections alter the conformer energy ordering slightly, the no-match conformers always stay in the lower energy group, leaving an unsolved question as to why these lower energy conformers with “folded-like” structures were not observed in the jet-cooled FTMW spectra.