Inertial Defect Research Articles

Ka-Band Rotational Spectroscopy of Succinimide and N-Chlorosuccinimide.

Succinimide and its derivatives are cyclic five-membered rings that appear in a variety of natural products and are widely used in organic synthesis. From a structural standpoint, succinimide contains an NH group in the ring which interacts with two adjacent carbonyl groups, pushing the ring structure toward planarity at the expense of increasing ring strain and eclipsing interactions among the out-of-plane hydrogen atoms in the two CH2 groups. Previous quantum chemical calculations at different levels of theory have predicted both a nonplanar C2 structure and a planar C2v structure, the latter of which is the most consistent with gas-phase electron diffraction measurements. Here, we report the pure rotational spectra of succinimide and N-chlorosuccinimide in the 26.5-40.0 GHz range using chirped-pulse Fourier transform microwave spectroscopy, supported by coupled cluster and density functional theory quantum chemical calculations. The spectra were fit to Watson's A-reduced effective Hamiltonian, including both 35Cl and 37Cl isotopologues of N-chlorosuccinimide as well as the N and Cl quadrupole hyperfine interactions. On the basis of the agreement with quantum chemical calculations and the measured inertial defects, we find that the rotational spectra are consistent with a planar ring structure, with a maximum out-of-plane angle of ≤5°.

Conformational Landscapes of 2,3-, 2,4-, 2,5-, and 2,6-Difluorobenzaldehyde Unveiled by Rotational Spectroscopy.

We report the coexistence of anti-conformers and energetically unfavorable syn-conformers of 2,3-, 2,4-, 2,5-, and 2,6-difluorobenzaldehyde in the gas phase using broadband chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy. The rotational spectra of monosubstituted 13C isotopologues of the anti-conformers have also been assigned in natural abundance, which were used to derive their vibrationally averaged geometries and semi-experimental equilibrium structures. The energy differences between anti- and syn-conformations are estimated to be 10.9, 11.3, and 12.9 kJ/mol for 2,3-, 2,4-, and 2,5-difluorobenzaldehyde, respectively, at the theoretical level of DLPNO-CCSD(T)/def2-TZVP. Despite the steric repulsion caused by the close proximity between the oxygen atom of the aldehyde group and the ortho-substituted fluorine atom, our experimental results indicate the planarity of the syn-conformations. The frequencies of the large amplitude torsion between the phenyl and aldehyde groups have been estimated by experimental inertial defects, which agree with theoretical calculation results.

High-resolution infrared spectroscopy of jet cooled cyclobutyl in the α-CH stretch region: large-amplitude puckering dynamics in a 4-membered ring radical.

Gas-phase cyclobutyl radical (c-C4H7) is generated at a rotational temperature of Trot = 26(1) K in a slit-jet discharge mixture of 70% Ne/30% He and 0.5-0.6% cyclobromobutane (c-C4H7Br). A fully rovibrationally resolved absorption spectrum of the α-CH stretch fundamental band between 3062.9 cm-1 to 3075.7 cm-1 is obtained and analyzed, yielding first precision structural and dynamical information for this novel radical species. The α-CH stretch band origin is determined to be 3068.7887(4) cm-1, which implies only a modest (≈0.8 cm-1) blue shift from rotationally unresolved infrared spectroscopic studies of cyclobutyl radicals in liquid He droplets [A. R. Brown, P. R. Franke and G. E. Douberly, J. Phys. Chem. A, 2017, 121, 7576-7587]. Of particular dynamical interest, a one-dimensional potential energy surface with respect to the ring puckering coordinate is computed at CCSD(T)/ANO2 level of theory and reveals a double minimum Cs puckered geometry, separated by an exceedingly shallow planar C2v transition state barrier (Ebarr ≈ 1 cm-1). Numerical solutions on this double minimum potential yield a zero-point energy for the ground state (Ezero-point ≈ 27 cm-1) greatly in excess of the interconversion barrier. This is indicative of highly delocalized, large amplitude motion of the four-membered ring structure, for which proper vibrationally averaging of the moment of inertia tensor reproduces the experimentally determined inertial defect remarkably well. Finally, intensity alternation in the experimental spectrum due to nuclear spin statistics upon exchange of three indistinguishable H atom pairs (IH = ½) matches Ka + Kc = even : odd = 36 : 28 predictions, implying that the unpaired electron in the radical center lies in an out-of-plane pπ orbital. Thus, high-resolution infrared spectroscopy provides first experimental confirmation of a shallow double minimum ring puckering potential with a highly delocalized ground state wave function peaked at a planar C2v transition state geometry consistent with a cyclobutyl π radical.

The Microwave Rotational Electric Resonance (RER) Spectrum of Benzothiazole.

The microwave spectra of benzothiazole were measured in the frequency range 2-26.5 GHz using a pulsed molecular jet Fourier transform microwave spectrometer. Hyperfine splittings arising from the quadrupole coupling of the 14N nucleus were fully resolved and analyzed simultaneously with the rotational frequencies. In total, 194 and 92 hyperfine components of the main species and the 34S isotopologue, respectively, were measured and fitted to measurement accuracy using a semi-rigid rotor model supplemented by a Hamiltonian accounting for the 14N nuclear quadrupole coupling effect. Highly accurate rotational constants, centrifugal distortion constants, and 14N nuclear quadrupole coupling constants were deduced. A large number of method and basis set combinations were used to optimize the molecular geometry of benzothiazole, and the calculated rotational constants were compared with the experimentally determined constants in the course of a benchmarking effort. The similar value of the χcc quadrupole coupling constant when compared to other thiazole derivatives indicates only very small changes of the electronic environment at the nitrogen nucleus in these compounds. The small negative inertial defect of -0.056 uÅ2 hints that low-frequency out-of-plane vibrations are present in benzothiazole, similar to the observation for some other planar aromatic molecules.

Radiation-free and non-Hermitian topology inertial defect states of on-chip magnons

Radiative damping is a strong dissipation source for the quantum emitters hybridized with propagating photons, electrons, or phonons, which is not easily avoidable for on-chip magnonic emitters as well that can radiate via the surface acoustic waves of the substrate. Here we demonstrate in an array of on-chip nanomagnets coupled in a long range via exchanging the surface acoustic waves that a point defect in the array, which can be introduced by the local magnon frequency shift by a local biased magnetic field or the absence of a magnetic wire, strongly localizes the magnons, in contrast to the well spreading Bloch-like collective magnon modes in such an array setting. The radiation of the magnon defect states is exponentially suppressed by the distance of the defect to the array edges. Moreover, this defect state is strikingly inertial to the non-Hermitian topology that localizes all the extended states at one boundary. Such configuration robust magnon defect states towards radiation-free limit may be suitable for high-fidelity magnon quantum information storage in the future on-chip magnonic devices.

The hydration of an oxy-polycyclic aromatic compound: the case of naphthaldehyde.

The study of the intermolecular interactions of polycyclic aromatic compounds, considered as important pollutants of the Earth's atmosphere since they are emitted by the partial combustion of fuels, is essential to understand the formation and aging of their aerosols. In this study, the hydration of α-naphthaldehyde and β-naphthaldehyde isomers was investigated through a combination of Fourier transform microwave spectroscopy and quantum chemical calculations. Monohydrate structures were observed experimentally for both isomers, with two hydrate structures observed for β-naphthaldehyde and only one for α-naphthaldehyde, consistent with computational predictions. Analysis of the monohydrate structures indicated that the β-isomer exhibits higher hydrophilicity compared to the α-isomer, supported by electronic densities, hydration energies, and structural considerations. Further computational calculations were conducted to explore the planarity of the naphthaldehyde hydrates. Different levels of theory were employed, some of these revealing slight deviations from planarity in the hydrate structures. Low-frequency out-of-plane vibrational modes were examined, and the inertial defect was used to assess the planarity of the hydrates. The results suggested that the hydrates possess a predominantly planar structure, in agreement with the highest level of computational calculations and the absence of c-type transitions in the experimental spectra. Additionally, calculations were extended to dihydrate structures by attaching two water molecules to the naphthaldehyde isomers. The most stable dihydrate structures were predicted to be combinations of the observed monohydrate positions. However, experimental observation of the most stable dihydrate structures was challenging due to their very low vapour pressure, calling for complementary experiments using laser ablation nozzles.

Electronic, vibrational, and rotational analysis of 1,2-benzanthracene by high-resolution spectroscopy referenced to an optical frequency comb.

The electronic and vibrational structures of 1,2-benzanthracene-h12 (aBA-h12) and 1,2-benzanthracene-d12 (aBA-d12) were elucidated by analyzing fluorescence excitation spectra and dispersed fluorescence spectra in a supersonic jet on the basis of DFT calculation. We also observed the high-resolution and high-precision fluorescence excitation spectrum of the S1←S000 0 band, and determined the accurate rotational constants in the zero-vibrational levels of the S0 and S1 states. In this high-resolution measurement, we used a single-mode UV laser whose frequencies were controlled with reference to an optical frequency comb. The inertial defect is negligibly small, the molecule is considered to be planar, and the obtained rotational constants were well reproduced by the equation-of-motion coupled cluster singles and doubles (EOM-CCSD) calculation. Both a-type and b-type transitions are found to be included in the rotationally resolved spectrum, and the a-type contribution is dominant, that is, the transition moment is nearly parallel to the long axis of the aBA molecule. We concluded that the S1 state is mainly composed of the Φ(B) configuration. The observed fluorescence lifetime (106ns) is considerably longer than that of the Φ(A) system, such as anthracene (18ns). The transition moment for the lower state of mixed states becomes small, reflecting a near-cancelation of the contributions from the parts of the wavefunction corresponding to the two electronic configurations. The bandwidth of the S2 ← S0 transition is large, and the structure is complicated. It is attributed to vibronic coupling with the high vibrational levels of the S1 state.

Chirped-pulse Fourier-transform millimeter-wave rotational spectroscopy of furan in its v10 and v13 excited vibrational states

Furan, a prototypical heteroaromatic cyclic ether, is an important molecule that has garnered attention from a wide range of fields, from food and health research to combustion and atmospheric chemistry. Chirped-pulse Fourier-transform rotational spectroscopy of jet-cooled furan in the W-band across three narrow regions 79.3–79.45 GHz, 88.6–88.8 GHz, and 97.95–98.15 GHz is reported here. A pyrolysis nozzle was used to efficiently populate vibrationally excited states of low-frequency modes. Apart from the v = 0 state, vibrationally excited v = 1 states of modes v11, v14, v10, and v13 were observed. Furan is a planar molecule and these observed excited state modes correspond to out-of-plane vibrations. The v = 0 state and the vibrationally excited v11 and v14 were previously recorded and fit by Barnum et al (T. J. Barnum, K. L. K. Lee, B. A. McGuire, ACS Earth Space Chem. 5 (2021), 2986–2994). Rotational transitions in the J”=5 to 9 rotational states were fit for the previously undetected v10 mode and experimental linelists for v = 1 states of modes v10 and v13 are provided, both of which are out-of-plane CH bending modes. Inertial defect was shown to be a useful quantity to extract structural information of vibrational modes of planar asymmetric tops. These rotational fits will assist astronomical searches for furan and its vibrational states.

Self-rotation regulates interface evolution in biphasic active matter through taming defect dynamics.

Chirality can endow nonequilibrium active matter with unique features and functions. Here, we explore the chiral dynamics in biphasic active nematics composed of self-rotating units that continuously inject energy and angular momentum at the microscale. We show that the self-rotation of units can regularize the boundaries between two phases, rendering sinusoidal-like interfaces, which allow lateral wave propagation and are characterized by chains of ordered antiferromagnetic cross-interface flow vortices. Through the spontaneous coordination of counter-rotating units across the interfaces, topological defects excited by activity are sorted spatiotemporally, where positive defects are locally trapped at the interfaces but, unexpectedly, are transported laterally in a unidirectional rather than wavy mode, whereas inertial negative defects remain spinning in the bulks. Our findings reveal that individual chirality could be harnessed to modulate interfacial morphodynamics in active systems and suggest a potential approach toward controlling topological defects for programmable microfluidics and logic operations.

Further rotational spectroscopy of phenol: Sextic centrifugal distortion and vibrational satellites

The room temperature rotational spectrum of phenol has been reinvestigated at 8–18 GHz with a waveguide Fourier transform microwave spectrometer and at 90–137 GHz with a harmonic generation spectrometer. The supersonic expansion spectrum was also measured at 9–18 GHz with a cavity Fourier transform microwave spectrometer. The data sets for the ground state and the two lowest excited vibrational states have been considerably extended, resulting in significant improvement of the spectroscopic parameters. In particular, access to different transition types facilitated by the waveguide spectrometer allowed precise determination of sextic centrifugal distortion constants for the ground state and their intercomparison with computed values. Transitions in the next five higher vibrational states have been assigned and fitted for the first time, and the vibrational assignment was confirmed by computed inertial defects and vibrational changes in rotational constants.

Influence of π-electron conjugation outside the aromatic ring on the methyl internal rotation of 4-methyl-5-vinylthiazole

The microwave spectrum of 4-methyl-5-vinylthiazole was measured using a pulsed molecular jet Fourier transform microwave spectrometer operating in the frequency range from 2.0 to 26.5 GHz. Only the anti-conformer was observed. Due to internal rotation of the methyl group, doublets containing an A and an E torsional species were found for all rotational transitions. Hyperfine structures arising from the 14N nuclear quadrupole coupling were resolved. The complex spectral patterns were analysed and fitted using the XIAM and BELGI-Cs-hyperfine codes, yielding a barrier to methyl internal rotation of 107.0901(7) cm−1 and the quadrupole coupling constants = −3.545(13), = −1.563(24) and = 1.76(11) MHz. The experimental results were supported by data from quantum chemistry. Some calculations using the MP2 method yielded non-planar structures, where the vinyl group is tilted out of the thiazole ring plane. The inertial defect and the constant were compared with those obtained for other aromatic molecules to support the planarity of 4-methyl-5-vinylthiazole. A comparison of the methyl torsional barrier with other thiazole derivatives suggests that electrostatic effects caused by the π-conjugated system of thiazole extended by the vinyl group are the reason of the low barrier of the methyl group.

The microwave spectrum of the difluorocyanomethyl radical, ĊF2CN

The pure rotational spectrum of the open shell difluorocyanomethyl radical, ĊF2CN, has been measured using two Balle-Flygare-type cavity Fourier-Transform-Microwave (FTMW) spectrometers both equipped with pulsed discharge nozzles. A total of 156 transitions (from N = 1 – 0 to 6 – 5, and Ka = 0, 1, 2, 3) in the electronic ground state were observed between 6.5 GHz and 38.4 GHz with a typical linewidth of ∼5 kHz full-width-half-maximum. A Hamiltonian that included semi-rigid rotor, spin-rotation, and nuclear hyperfine parameters was fit to the observed data set and these parameters have been interpreted and compared to similar radicals. Excellent agreement between experimental and uB3LYP/aug-cc-pVQZ calculated rotational constants, the experimental inertial defect, −0.6858(2) uÅ2, and the failure of a coupling scheme in which the fluorine nuclei are treated as identical and related by a C2v symmetry axis combine to indicate a nonplanar structure for the ĊF2CN radical.

Microwave Spectrum of Two-Top Molecule: 2-Acetyl-3-Methylthiophene.

The microwave spectrum of 2-acetyl-3-methylthiophene (2A3MT) was recorded in the frequency range from 2 to 26.5 GHz using a molecular jet Fourier transform microwave spectrometer and could be fully assigned to the anti-conformer of the molecule, while the syn-conformer was not observable. Torsional splittings of all rotational transitions in quintets due to internal rotations of the acetyl methyl and the ring methyl groups were resolved and analyzed, yielding barriers to internal rotation of 306.184(46) cm-1 and 321.813(64) cm-1 , respectively. The rotational and centrifugal distortion constants were determined with high accuracy, and the experimental values are compared to those derived from quantum chemical calculations. The experimentally determined inertial defect supports the conclusion that anti-2A3MT is planar, even though a number of MP2 calculations predicted the contrary.

Ro-vibrationally averaged molecular structure of benzene: Why almost the same bond lengths are observed for the C H and C D bonds?

• Ro-vibrationally averaged structure of benzene is discussed in terms of local modes. • Different from aliphatics, r 0 , eff (C H) ≅ r 0 , eff (C D) in aromatic hydrocarbons. • This occurs due to the balance of stretch, out-of-plane, and in-plane bending motions of the C H bonds. • The conclusion is manifested by the negative value of the inertial defect. • Vibrationally averaged structure of the C H bonds region is non-flat with planar C 6 ring. Different from the well-established understanding that the C H bond length is longer than the C D bond length in the H(D)-isotopologues due to the anharmonicity of the potential, almost the same values of C H(D) bond lengths, derived from the experimental rotational constants, have been reported by Baba group for the cases of benzene, naphthalene, and anthracene H(D)-isotopologues. Taking benzene as an example, we show here that this unexpected, curious finding can be explained in terms of the ab initio stretching and bending potentials for each local mode. The explanation is based on the viewpoints that the experimental rotational constants correspond to the bond lengths projected onto each of the relevant principal-axis planes, and that on observation, we cannot distinguish the plus and minus bending angles in both out-of-plane ( L ⊥ ) and in-plane ( L ∥ ) bending local modes with respect to the C α H(D) α bond in [C 5 H(D) 5 C α ] H(D) α . The C α H(D) α stretching local mode ( L str ) gives, as usual, longer C α H α than C α D α bond-lengths due to its anharmonicity. However, in both L ⊥ and L ∥ modes, the vibrationally averaged bond-length projected onto the principal axis is shorter for C α H α than for C α D α due to the larger averaged bending angle for the former bond. When we consider the projected bond-lengths, these antithetical factors, i.e., one in the L str mode against the others in L ⊥ and L ∥ modes, nearly cancel, resulting in almost the same C H and C D bond lengths as is experimentally reported. The vibrationally averaged structure of benzene in the zero-point vibration state is predicted to be non-flat for the peripheral C H bonds region, which is confirmed from the theoretical and experimental values of the inertial defect.

Rotational spectroscopy and precise molecular structure of 1,2-dichlorobenzene

Supersonic expansion rotational spectroscopy at 4–18 GHz with rectangular pulse and chirp excitation was used to measure spectra of twelve isotopic species of 1,2-dichlorobenzene at conditions of completely resolved double chlorine hyperfine structure by using a newly constructed slit expansion nozzle. Four species: 37Cl13 and the three singly substituted 13C species have been assigned for the first time. Spectroscopic constants for six isotopic species with single deuterium substitution were considerably improved by using chemically synthesised samples. Hyperfine constants in the field gradient principal axes system were determined and used as a test of self-consistency of the analysis. Additional room-temperature measurements up to 275 GHz allowed assignment of rotational transitions in first excited states of the three lowest normal modes. The determined values of vibrational changes in rotational constants, inertial defects, and quartic and sextic centrifugal distortion constants, allowed calibration of harmonic and anharmonic force field calculations, resulting in determination, among others, of precise semi-experimental equilibrium, reSE, geometry of 1,2-dichlorobenzene. It is found that r(C-C) and ∠(C-C-C) in the phenyl ring of 1,2-dichlorobenzene show very small changes relative to benzene.

The Scent of Maibowle - π Electron Localization in Coumarin from Its Microwave-Determined Structure.

The microwave spectra of the natural substance coumarin, a planar aromatic molecule with the specific scent of maibowle, a popular fruit punch served in spring and early summer, were recorded using a molecular jet Fourier transform microwave spectrometer working in the frequency range from 4.0 to 26.5 GHz. The rotational constants and centrifugal distortion constants were determined with high precision, reproducing the spectra to experimental accuracy. The spectra of all singly-substituted 13 C and 18 O isotopologues were observed in their natural abundances to determine the experimental heavy atom substitution rs and semi-experimental equilibrium reSE structures. The experimental bond lengths and bond angles were compared to those obtained from quantum chemical calculations and those of related molecules reported in the literature with benzene as the prototype. The alternation of the C-C bond lengths to the value of 1.39 Å found for benzene reflects the localization of π electrons in coumarin, where the benzene ring and the lactone-like chain -CH=CH-(C=O)-O- are fused. The large, negative inertial defect of coumarin is consistent with out-of-plane vibrations of the fused rings.

Halogen bond and internal dynamics in the σ–complex of pyridine-chlorotrifluoromethane: A rotational study

The rotational spectrum of the 1:1 complex pyridine–chlorotrifluoromethane shows that the two moieties are held together through a CCl···N halogen bond (RCl···N = 2.909(5) Å). The quadrupolar effects of the 35Cl (or 37Cl) and 14N nuclei combined with the high density of the rotational transitions give rise to a very congested spectrum. The multidimensional large amplitude internal dynamics is reflected in a two times larger rotational constant A, on an unexpected positive values of the inertial defect of the ground state, and on a negative value of the DJ centrifugal distortion constant. This comes from a combination of a free internal rotation and of a very low energy in plane oscillation of CF3Cl with respect to pyridine. However, a coupled Hamiltonian including Coriolis interactions with an hypothetical (unobserved) v = 1 state solves the initial result of an unphysical negative value for the centrifugal distortion constant.

Microwave spectra and structures of 2-fluoro-4-picoline

Rotational spectrum of the ground state of 2-fluro-4-picoline has been investigated by pulsed jet Fourier transform microwave spectroscopy. Besides the parent species, all the mono-substituted 13C and 15N isotopologues in natural abundance have been also measured and assigned. The rotational spectrum displays the features of the quadrupole coupling effect of the 14N nucleus with a near-free internal rotation of CH3 top. The V3 barrier (191 (60) J/mol) to the internal rotation of CH3 has been estimated from the unexpected low values of the inertial defects.

2-Propionylthiophene: planar, or not planar, that is the question.

The long-standing ambiguity of the molecular planarity when an alkyl group is attached to a system with conjugated double bonds is a great challenge for both experiments and theory. This also holds true for the case of 2-propionylthiophene (2PT) where a propionyl group is attached at the second position of the planar, aromatic thiophene ring. Results from quantum chemistry at the MP2 level of theory, showing that in the two conformers syn- and anti-2PT the ethyl group of the propionyl moiety is slightly tilted out of the thiophene ring plane, conflict with those from the other methods, stating that the ethyl group is in-plane with the thiophene ring. In the microwave spectrum, both syn- and anti-2PT were observed, and their geometry parameters such as the rotational and quartic centrifugal distortion constants were precisely determined. The experimental heavy atom skeleton obtained by isotopic substitutions revealed a tiny, but non-zero tilt angle of the ethyl group out of the thiophene plane, thereby convincingly confirming the non-planarity of 2-propionylthiophene. This conclusion was further supported by the inertial defects calculated from the experimental rotational constants. Finally, splittings arising from the internal rotation of the terminal methyl group were analysed, yielding torsional barriers of 806.94(54) cm-1 and 864.5(88) cm-1 for the two observed conformers, respectively.

Pure rotational spectrum of cis-OSOO

Abstract Pure rotational transitions of cis-OSOO are identified in a discharge plasma of a SO2 and O2 gaseous mixture by Fourier-transform microwave (FTMW) and FTMW-MW double-resonance spectroscopy. Both a- and b-type transitions are observed for this molecule, and the rotational and centrifugal distortion constants are precisely determined from the observed line positions. The inertial defect calculated from the determined rotational constants indicates that the cis-OSOO molecule has a planar equilibrium geometry in the ground vibronic state.